EP2356095B2 - Methods of making cyclic, n-amino functional triamines - Google Patents
Methods of making cyclic, n-amino functional triamines Download PDFInfo
- Publication number
- EP2356095B2 EP2356095B2 EP09744802.1A EP09744802A EP2356095B2 EP 2356095 B2 EP2356095 B2 EP 2356095B2 EP 09744802 A EP09744802 A EP 09744802A EP 2356095 B2 EP2356095 B2 EP 2356095B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- catalyst
- aep
- cyclic
- eda
- amines
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 238000000034 method Methods 0.000 title claims description 57
- 125000004122 cyclic group Chemical group 0.000 title claims description 53
- 239000003054 catalyst Substances 0.000 claims description 99
- 238000006243 chemical reaction Methods 0.000 claims description 67
- 239000000376 reactant Substances 0.000 claims description 31
- 150000001875 compounds Chemical class 0.000 claims description 21
- 229910052759 nickel Inorganic materials 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 18
- -1 cyclic amine Chemical class 0.000 claims description 15
- 229910052702 rhenium Inorganic materials 0.000 claims description 14
- KSSJBGNOJJETTC-UHFFFAOYSA-N COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC Chemical compound COC1=C(C=CC=C1)N(C1=CC=2C3(C4=CC(=CC=C4C=2C=C1)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC(=CC=C1C=1C=CC(=CC=13)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)N(C1=CC=C(C=C1)OC)C1=C(C=CC=C1)OC)C1=CC=C(C=C1)OC KSSJBGNOJJETTC-UHFFFAOYSA-N 0.000 claims description 9
- 238000006798 ring closing metathesis reaction Methods 0.000 claims description 6
- 150000002825 nitriles Chemical group 0.000 claims description 4
- FZZMTSNZRBFGGU-UHFFFAOYSA-N 2-chloro-7-fluoroquinazolin-4-amine Chemical group FC1=CC=C2C(N)=NC(Cl)=NC2=C1 FZZMTSNZRBFGGU-UHFFFAOYSA-N 0.000 claims description 2
- IMUDHTPIFIBORV-UHFFFAOYSA-N aminoethylpiperazine Chemical compound NCCN1CCNCC1 IMUDHTPIFIBORV-UHFFFAOYSA-N 0.000 description 86
- 150000001412 amines Chemical class 0.000 description 70
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 64
- 239000000203 mixture Substances 0.000 description 59
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 58
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 41
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 33
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 description 33
- 238000005891 transamination reaction Methods 0.000 description 33
- 239000000047 product Substances 0.000 description 25
- 239000001257 hydrogen Substances 0.000 description 23
- 229910052739 hydrogen Inorganic materials 0.000 description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 239000002245 particle Substances 0.000 description 18
- 230000008569 process Effects 0.000 description 18
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 17
- 229910021529 ammonia Inorganic materials 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- VILCJCGEZXAXTO-UHFFFAOYSA-N 2,2,2-tetramine Chemical compound NCCNCCNCCN VILCJCGEZXAXTO-UHFFFAOYSA-N 0.000 description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 12
- 239000006227 byproduct Substances 0.000 description 11
- 229910052751 metal Inorganic materials 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 125000003277 amino group Chemical group 0.000 description 9
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 239000002638 heterogeneous catalyst Substances 0.000 description 8
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- 239000002243 precursor Substances 0.000 description 8
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 description 8
- 101100205030 Caenorhabditis elegans hars-1 gene Proteins 0.000 description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 7
- 125000002947 alkylene group Chemical group 0.000 description 7
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 7
- 239000000377 silicon dioxide Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 238000006356 dehydrogenation reaction Methods 0.000 description 6
- 239000012467 final product Substances 0.000 description 6
- 238000001354 calcination Methods 0.000 description 5
- 239000000470 constituent Substances 0.000 description 5
- 150000002431 hydrogen Chemical class 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- LHIJANUOQQMGNT-UHFFFAOYSA-N aminoethylethanolamine Chemical compound NCCNCCO LHIJANUOQQMGNT-UHFFFAOYSA-N 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 239000010955 niobium Substances 0.000 description 4
- 239000008188 pellet Substances 0.000 description 4
- 125000004193 piperazinyl group Chemical group 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 239000012429 reaction media Substances 0.000 description 4
- 238000006268 reductive amination reaction Methods 0.000 description 4
- 238000007363 ring formation reaction Methods 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000004593 Epoxy Substances 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 230000002378 acidificating effect Effects 0.000 description 3
- 238000005576 amination reaction Methods 0.000 description 3
- 238000009833 condensation Methods 0.000 description 3
- 230000005494 condensation Effects 0.000 description 3
- 238000005470 impregnation Methods 0.000 description 3
- 229910052742 iron Inorganic materials 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical class 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 229910003455 mixed metal oxide Inorganic materials 0.000 description 3
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 229910052758 niobium Inorganic materials 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 150000004760 silicates Chemical class 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000004721 Polyphenylene oxide Chemical group 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical group [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 2
- 239000003377 acid catalyst Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 125000000217 alkyl group Chemical group 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 239000012298 atmosphere Substances 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000010924 continuous production Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000001923 cyclic compounds Chemical class 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052741 iridium Inorganic materials 0.000 description 2
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 239000011733 molybdenum Substances 0.000 description 2
- WBIWIXJUBVWKLS-UHFFFAOYSA-N n'-(2-piperazin-1-ylethyl)ethane-1,2-diamine Chemical compound NCCNCCN1CCNCC1 WBIWIXJUBVWKLS-UHFFFAOYSA-N 0.000 description 2
- BETVNUCOOCCCIO-UHFFFAOYSA-N n-(2-dimethoxyphosphinothioylsulfanylethyl)acetamide Chemical compound COP(=S)(OC)SCCNC(C)=O BETVNUCOOCCCIO-UHFFFAOYSA-N 0.000 description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 2
- BKIMMITUMNQMOS-UHFFFAOYSA-N nonane Chemical compound CCCCCCCCC BKIMMITUMNQMOS-UHFFFAOYSA-N 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 229910052762 osmium Inorganic materials 0.000 description 2
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 2
- 125000005702 oxyalkylene group Chemical group 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 235000021317 phosphate Nutrition 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229920000570 polyether Chemical group 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 229910052703 rhodium Inorganic materials 0.000 description 2
- 239000010948 rhodium Substances 0.000 description 2
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 150000003512 tertiary amines Chemical class 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- AGGKEGLBGGJEBZ-UHFFFAOYSA-N tetramethylenedisulfotetramine Chemical compound C1N(S2(=O)=O)CN3S(=O)(=O)N1CN2C3 AGGKEGLBGGJEBZ-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- 229910052726 zirconium Inorganic materials 0.000 description 2
- VOZKAJLKRJDJLL-UHFFFAOYSA-N 2,4-diaminotoluene Chemical group CC1=CC=C(N)C=C1N VOZKAJLKRJDJLL-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 235000013162 Cocos nucifera Nutrition 0.000 description 1
- 244000060011 Cocos nucifera Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000004606 Fillers/Extenders Substances 0.000 description 1
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- MBYLVOKEDDQJDY-UHFFFAOYSA-N NCCN(CCN)CCN Chemical compound NCCN(CCN)CCN MBYLVOKEDDQJDY-UHFFFAOYSA-N 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 1
- 229920002873 Polyethylenimine Polymers 0.000 description 1
- 239000007868 Raney catalyst Substances 0.000 description 1
- 229910000564 Raney nickel Inorganic materials 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 229910052768 actinide Inorganic materials 0.000 description 1
- 150000001255 actinides Chemical class 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000002015 acyclic group Chemical group 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000004703 alkoxides Chemical class 0.000 description 1
- 125000005263 alkylenediamine group Chemical group 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- 125000003710 aryl alkyl group Chemical group 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 125000000732 arylene group Chemical group 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000740 bleeding effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 238000003965 capillary gas chromatography Methods 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000011246 composite particle Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- UYMKPFRHYYNDTL-UHFFFAOYSA-N ethenamine Chemical compound NC=C UYMKPFRHYYNDTL-UHFFFAOYSA-N 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 229910052733 gallium Inorganic materials 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002466 imines Chemical class 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 230000009878 intermolecular interaction Effects 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 229910052747 lanthanoid Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- HCWCAKKEBCNQJP-UHFFFAOYSA-N magnesium orthosilicate Chemical compound [Mg+2].[Mg+2].[O-][Si]([O-])([O-])[O-] HCWCAKKEBCNQJP-UHFFFAOYSA-N 0.000 description 1
- 239000000391 magnesium silicate Substances 0.000 description 1
- 229910052919 magnesium silicate Inorganic materials 0.000 description 1
- 235000019792 magnesium silicate Nutrition 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 150000002736 metal compounds Chemical class 0.000 description 1
- 229910052914 metal silicate Inorganic materials 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- CNHRNMLCYGFITG-UHFFFAOYSA-A niobium(5+);pentaphosphate Chemical compound [Nb+5].[Nb+5].[Nb+5].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O CNHRNMLCYGFITG-UHFFFAOYSA-A 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 125000002560 nitrile group Chemical group 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000003415 peat Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 229920001281 polyalkylene Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 239000004848 polyfunctional curative Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- CGFYHILWFSGVJS-UHFFFAOYSA-N silicic acid;trioxotungsten Chemical compound O[Si](O)(O)O.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1.O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 CGFYHILWFSGVJS-UHFFFAOYSA-N 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 230000017105 transposition Effects 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 239000012000 urushibara nickel Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 229910001868 water Inorganic materials 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/12—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms
- C07D295/125—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
- C07D295/13—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by singly or doubly bound nitrogen atoms with the ring nitrogen atoms and the substituent nitrogen atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings to an acyclic saturated chain
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D241/00—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings
- C07D241/02—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings
- C07D241/04—Heterocyclic compounds containing 1,4-diazine or hydrogenated 1,4-diazine rings not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
Definitions
- the present invention relates to processes for making cyclic triamines using transamination techniques.
- the cyclic triamines are made from higher amine precursors via ring closure reactions in the presence of a suitable catalyst.
- Cyclic triamines such as aminoethylpiperazine (“AEP,”) have many industrial uses. For instance, these compounds are useful as dispersants, epoxy curing agents, chelants, catalysts, accelerators, hardeners, extenders in polymer fabrication, starting materials in the preparation of other amines, starting materials for making pesticides, and the like.
- AEP aminoethylpiperazine
- AEP is also known by other names including 2-piperazin-1-ylethaneamine; 2-(1-piperazinyl) ethylamine; N-AEP, N-(2-aminoethyl) piperazine; 2-piperazinoethylamine; 1-(2-aminoethyl)piperazine, 1-piperazine ethaneamine, and 1-aminoethylpiperazine.
- AEP is a by-product formed from the reaction of ethylenedichloride (EDC) and ammonia or amines to form higher amines. See, e.g., Russian Patent Documents 2226188 and 2186761 and also Khimicheskaya Promyshlennost (Moscow; Russian Federation) (1987), (5) 267-9 .
- EDC ethylenedichloride
- Khimicheskaya Promyshlennost Moscow; Russian Federation (1987), (5) 267-9 .
- the amount of AEP produced generally is small relative to the entire product mix. Also, undue amounts of salts can also result. Excessive salt production can complicate purification and/or disposal.
- Cyclic triamines can also be formed by reacting hydroxyl functional reactants (e.g., monoethanolamine or ethylene glycol) and/or amines with other amines or ammonia in the presence of acid catalysts at high temperatures, e.g., 300°C or higher.
- Acid catalysts include, for example, phosphorous doped, niobium doped, or tungsten doped metal oxides and several mixed metal oxides including zeolites.
- PIP piperazine
- EDA ethylenediamine
- US 5073635 shows examples of monoethanolamine (MEA) and PIP (1/1 mole ratio) with other metal silicates (Y, La, Ce, Nb, Zr, Ti) with conversions of ⁇ 20-40% and AEP selectivities of 70-84%.
- US 5030740 teaches the use of tungsten oxide/titania for conversion of crude piperazine and MEA to AEP.
- selectivity to AEP is lower in part due to the high MEA/PIP ratio of 1:3, the relatively high conversion of MEA, and the reaction of EDA and diethylenetriamine (DETA) with MEA.
- DETA diethylenetriamine
- US 4927931 has examples based on niobium oxide and niobium phosphate catalysts. Selectivity is lower than with the silicates.
- US 5225599 discloses a process for the preparation of triethylenetetramine and N-(2-aminoethyl)ethanolamine .
- This process comprises the condensation of an alkyleneamine and an alkylene glycol in the presence of a condensation catalyst selected from Group IVB oxides or Group VIB compounds and a catalyst promoter.
- a mixture of silicotungstic acid (18 g), H2O, and TiO2/WO3 (55 g) was heated to 350 to give a catalyst.
- a mixture of ethylenediamine and ethylene glycol (2.95 mol ratio) was fed into a tube containing the above catalyst at 269.8 and 614.7 psig to give a product containing 6.13% by weight piperazine, 18.71 % by weight triethylenetetramine, 47.84% by weight N-(2-aminethyl)ethanolamine; and 2.39% by weight N-(2-aminoethyl)piperazine, and 24.93% by weight other products.
- US 4906782 discloses a process whereby alkyleneamines having an increased number of alkylene units are prepared by reacting NH 3 and/or an alkyleneamine with an alkanolamine in the presence of a Nb-containing catalyst insoluble or slightly soluble in the aqueous reaction solution.
- Ethylenediamine 90, monoethanolamine 45, and NbO5 1.4 g were heated at 300 for 5 to give piperazine 2.3, diethylenetriamine 59.8, N-(2-aminoethyl)ethanolamine 2.6, N-(2-aminoethyl)piperazine 1.0, triethylenetetramine (isomers) 15.0, tetraethylenepentamine (isomers) 2.0, and pentaethylenehexamine (isomers) 1.0%, vs. 0.1, 76.0, 23.8, 0, 0, 0, 0, respectively, when using silica-alumina in place of NbO5.
- amines esp. acyclic polyalkylenepolyamines
- amines are prepared by amination of alcohols with reactant amines in the presence of H 2 and binary or ternary compounds of Group VIB metals as catalysts.
- US 4806517 shows that linear polyethylenepolyamines are prepared by the condensation of ethylenediamine (I) with ethanolamine (II) over a catalyst which is prepared by impregnating Group IVB element oxide pellets with an aqueous solution of a P-O compd. at 20-150°C so as to bond 0.5-6% of the P to the surface of the pellets in the form of hydroxy-containing phosphate groups, and then calcining at 200-900.
- a 100 mL solution of 85% H3PO4 was heated to 130°C under an inert atmosphere,105 cm3 of TiO2 pellets were added, the mixture reacted for 2 h, and calcined at 600°C for 16 h.
- the catalyst was contacted with a 2:1 molar ratio I-II mixt. of 325, producing approximately 65% II conversion with the formation (selectivity %) of piperazine 1.8, diothylenetriamine 59.0, N-(2-aminoethyl)ethanolamine 0.7, N-(2-aminoethyl)piperazine and N-(hydroxyethylpiperazine 2.1, triethylenetetramine 19.6, and tetraethylenepentamine 4.2%.
- Polyethylenepolyamines are prepared with high selectivity to linear products, from ethylenediamine (I) and ethanolamine (II) using activated C catalysts (optionally pretreated with strong mineral acids).
- Predominantly linearly extended polyalkylene polyamines are produced by treating alkylenediamines with alkylene glycols or alkanolamines using a P amide catalyst.
- the present invention provides strategies for making cyclic triamines. It has been discovered that reactant media including certain precursors and/or certain types of catalysts can be converted into cyclic triamines with improved conversion and selectivity.
- the strategies can be incorporated into reactions that involve transamination mechanisms. In the case of transamination, for instance, using transamination to self-cyclize higher amines of the type including at least four amine moieties in the presence of a suitable catalyst leads to desired cyclic triamines with notable conversion and yield.
- Preferred embodiments can produce reaction mixtures that are generally free of salt by-products.
- the present invention relates to a method of making a cyclic triamine of the type comprising first and second nitrogen backbone atoms and an N-amino moiety pendant from at least one of.the nitrogen backbone atoms, comprising the steps of:
- the present invention relates to a method of making a cyclic triamine of the type comprising first and second nitrogen backbone atoms and an N-amino moiety pendant from at least one of the nitrogen backbone atoms, comprising the steps of:
- the present invention provides a strategy for making cyclic triamines of the type comprising first and second nitrogen backbone atoms and an N-amino moiety pendant from at least one of the nitrogen backbone atoms.
- the amine groups of the triamine can be primary, secondary, tertiary, or a combination of these.
- the cyclic triamine can be fully saturated or may include double bonds in the backbone of the cyclic moiety and/or in a moiety pendant from the cyclic moiety.
- Cyclic triamines may be substituted or non-substituted. As used herein "substituted” means that a moiety other than H is pendant to the backbone. "Non-substituted” means that, other than the N-amino moiety(ies), other substituents of the backbone are hydrogen.
- cyclic triamines of the present invention are represented by the formula shown in Fig. 1 , wherein each of R 1 , R 5 , and R 6 is independently a monovalent moiety or co-member of a ring structure but do not include N as a constituent of an amine moiety. Any of R 1 , R 5 , and R 6 may optionally include one or more heteroatoms other than N in the backbone or a moiety pendant from the backbone.
- moieties suitable as R 1 , R 3 , and R 6 include but are not limited to H; linear, branched, or cyclic hydrocarbyl such as alkyl, aryl, aralkyl, or the like; a monovalent moiety including one or more heteroatoms; polyether chains comprising one or more oxyalkylene repeating units such as -R 17 O-, wherein R 17 is often alkylene of 2 to 5 carbon atoms; other oligomeric or polymer chains of at least 2 repeating units; -R 18 N- wherein R 18 is alkylene of at least 2, preferably 2 to 5 carbon atoms.
- each of R 1 , R 5 , and R 6 independently is H or straight, branched, or cyclic hydrocarbyl such as alkyl of 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. More preferably, each of R 1 , R 5 , and R 6 is H.
- Each of R 2 , R 3 , and R 4 is independently any suitable divalent moiety that may be substituted or unsubstituted.
- suitable divalent moieties include linear, branched, or cyclic hydrocarbylene moieties such as alkylene, arylene, aralkylene, or the like; polyether chains comprising one or more oxyalkylene repeating units such as -R 17 -, wherein R 17 is often alkylene of 2 to 5 carbon atoms; other oligomeric or polymer chains of at least 2 repeating units; and/or -R 18 N- wherein R 18 is alkylene of at least 2, preferably 2 to 5 carbon atoms.
- each of R 2 , R 3 , and R 4 is independently an alkylene moiety of 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, often ethylene.
- R 1 , R 2 , R 3 , R 4 , R 5 , or R 6 may be masked in accordance with conventional masking strategies to protect them in the course of the reaction described herein. After the reaction is completed, the functional groups can be unmasked if desired.
- the cyclic moiety incorporated into the cyclic triamine is a six-membered ring in which the two nitrogen backbone atoms are at positions 1 and 4 relative to each other in the ring and each nitrogen respectively constitutes a portion of an amine moiety.
- the other 4 atoms in the ring are carbon atoms.
- an N-amino moiety is linked to at least one of these backbone nitrogens.
- a six-membered ring will be referred to herein as a piperazine moiety.
- a cyclic triamine incorporating a piperazine moiety has the formula shown in Fig.
- each of R 7 through R 14 is independently a monovalent moiety or a co-member of a ring structure.
- each of R 7 and R 14 is independently a monovalent moiety according to the definitions of R 1 , R 5 , and R 6 .
- each of R 7 through R 14 are hydrogen such that the cyclic amine has the formula shown in Fig. 3 .
- the cyclic triamine is aminoethylpiperazine of the formula shown in Fig. 4 .
- This compound is commonly referred to as "AEP” and is unique for including a primary, secondary, and tertiary amine.
- AEP has many uses that include inhibition of corrosion, epoxy curing, surface activating, constituent of asphalt adhesive, mineral processing aid, and the like.
- AEP is also known by other names, including 2-piperazin-1-ylethaneamine; 2-(1-piperazinyl) ethylamine; N-AEP, N-(2-aminoethyl) piperazine; 2-piperazinoethylamine; 1-(2-aminoethyl)piperazine, 1-piperazine ethaneamine, and 1-aminoethylpiperazine.
- cyclic triamines are formed by reacting one or more suitable precursors under conditions effective to achieve the desired product.
- Transamination techniques are used to convert amines having four or more amine moieties (hereinafter "higher amines") into the desired cyclic triamine.
- Transamination techniques are used to form cyclic triamines from a wide range of precursors in the presence of a catalyst comprising Ni and Re.
- conversion refers to the total weight percentage of reactant lost as a result of reactions.
- the conversion can vary depending upon factors such as the reactants, catalyst, process conditions, and the like. In many embodiments, the conversion is at least 2 weight percent, preferably at least 10 weight percent, more preferably at least 25 weight percent, most preferably at least 35 weight percent.
- selectivity refers to the weight percentage of converted reactant(s) that form a desired cyclic triamine. Like conversion, selectivity will vary based upon factors including the reactants, catalyst, process conditions, and the like. In the practice of the present invention, selectivity for forming cyclic triamine in more preferred embodiments is at least 10%, preferably at least 25%, more preferably at least 50%.
- the reaction occurs at moderate temperature with a moderate resultant impurity load.
- Many leftover reactants, if any, and by-products, if any, have commercial value independent of the desired cyclic triamine product.
- the remaining product mixture has many uses, including being recycled as a feed for the cyclization reaction, refined to recover some of the product(s) in more pure form, used as reactants in other reactions, used as is or with any desired modification as products such as epoxy curing agents, combinations of these, and the like.
- the methods of the invention can be practiced in any suitable reactor. These include batch reactors, continuous fixed bed reactors, slurry bed reactors, fluidized bed reactors, catalytic distillation reactors, combinations of these, and the like.
- a higher amine is self-cyclized to from the cyclic triamine in the presence of a suitable catalyst via transamination techniques.
- Transamination generally refers to the transfer of one amine from one location to another.
- an amine moiety is transferred from one molecule to the other.
- a molecule is self-cyclized by reacting with itself, there is a transposition of an amino group within the molecule.
- the reaction can be viewed as causing one of the amine moieties to be removed from the molecule, allowing the other amine to bond to the location vacated by the removed amine group.
- the polyfunctional compounds used in the transamination reaction of the present invention can include a combination of primary, secondary, and tertiary amine moieties, but it is desirable if at least two of the amine moieties are primary and/or secondary to facilitate self-cyclization.
- Reactants can include a combination of one or more of such higher amines.
- the higher amine in many embodiments is linear or branched.
- a representative class of linear higher amines may be represented by the general formula of the following class of tetraamines shown in Fig.
- a linear tetraamine has the formula shown in Fig. 6 , wherein each of R 2 R 3 , and R 4 is each independently as defined above.
- a linear tetraamine has the formula shown in Fig. 7 .
- This compound is known as linear triethylenetetraamine or L-TETA.
- a representative class of branched higher amines may be represented by the general formula of the following class of tetraamines shown in Fig. 8 , wherein each of R 2 , R 3 , R 4 , R 5 , and R 6 is independently as defined above, and R 17 is a monovalent moiety according to the definitions for R 1 , R 5 , and R 6 above.
- a branched tetraamine has the formula shown in Fig. 9 , wherein each of R 2 , R 3 , and R 4 is each independently as defined above.
- a linear tetraamine has the formula shown in Fig.10 .
- This compound is known as trisaminoethylamine (TAEA).
- TEPA trisaminoethylamine
- PEHA pentaethylenepentaamine
- HPA heavy polyethyleneamines
- a suitable reaction medium might include a combination of L-TETA and TAEA wherein the weight ration of L-TETA to TAEA is in the range from 1:1000 to 1000:1, preferably 1:50 to 50:1, or even 1:5 to 5:1.
- L-TETA weight ration of L-TETA to TAEA
- one or more other higher amines could be used as well, including those that are monomeric, oligomeric, or polymeric.
- an oligomer refers to a compound incorporating 2 to 10 monomeric residues.
- a polymer refers to a compound incorporating more than 10 monomeric residues.
- a reaction medium comprising one or more higher amine reactants is self cyclized.
- L-TETA and/or TAEA can be self-cyclized to produce AEP with ammonia as a by-product.
- a pentaamine such as TEPA can be self-cyclized to produce AEP with ethylenediamine (EDA) as a by-product.
- EDA ethylenediamine
- the higher amine reactant(s) used in the self-cyclizing reaction can be supplied in substantially pure form or can be present with other ingredients, including other amines.
- an output of an exemplary industrial process may be a mixture including one or more amines including at least one higher amine, desirably at least one of L-TETA and/or TAEA.
- Such mixture might even include a desired cyclic triamine such as some AEP.
- Such a mixture can be used as a reactant mixture in the practice of the invention.
- the product mixture will be enriched with cyclic triamine content relative to the starting reaction medium.
- an illustrative output of an industrial process might include ethylenediamine (EDA), piperazine (PIP), diethylenetriamine (DETA), AEP, L-TETA, N-(Piperazinoethyl)ethylenediamine (PEEDA), Tetraethylenepentamine (L-TEPA), and others.
- EDA ethylenediamine
- PIP piperazine
- DETA diethylenetriamine
- AEP L-TETA
- L-TEPA Tetraethylenepentamine
- This mixture can be processed in the practice of the present invention to increase the AEP content.
- one or more of the amines of such a starting mixture, including the AEP can be removed prior to being subjected to the transamination reaction. Examples of enriching the AEP content of such a mixture and other mixtures as well are provided below.
- Nitrile functional amine precursors can also be used in the transamination methodologies.
- the nitrile groups can react with amines to give cyclic compounds, or may be converted to imines which can react with amines to give cyclic compounds or be reduced to the amine which can then proceed to cyclize via transamination.
- the amine mixture used as a starting reaction material for transamination will be in liquid form such that no additional solvent is needed. Indeed, in many instances it may be preferred to carry out the desired reaction in the absence of solvent. However, one or more solvents may be used if desired. A variety of solvents or combinations of solvents may be used. Desirably, the solvent is not unduly reactive with the higher amine reactant(s) or cyclic triamine product(s) and does not unduly decompose under the reaction conditions.
- solvents that could be used include saturated hydrocarbons such as pentane, hexane, octane, nonane, decane, or the like; aromatic hydrocarbons such as toluene, benzene, xylene, esther, combinations of these, and the like. Alcohols are desirably avoided, as many of these are capable of reacting with the amine reactants and/or products. If present, the amount of solvent used may vary over a wide range. In a typical instance, the solvent may constitute from 5 to 98 weight percent, desirably 10 to 80 weight percent, of the mixture.
- the reaction medium can be diluted to favor intramolecular reactions and, hence, cyclization, relative to intermolecular interactions.
- Catalysts can be acidic, alkaline, neutral, or a combination of different catalysts can be used.
- Representative classes of catalyst metals, alloys, intermetallic compositions, or molecules such as oxides, nitrides, phosphates, silicates, and the like, or mixtures of one or more transition metals, including the lanthanoid and/or actinoid series.
- a wide variety of catalysts applicable to amine chemistry are described in U.S. Pat. Nos.
- the catalyst(s) can be present as metals, alloys, mixtures, intermetallic compositions, as compounds such as oxides, hydroxides, salts, alkoxides, silicates, phosphates, as complexes, or the like.
- the catalyst incorporates one or more hydrogenation and/or dehydrogenation catalysts.
- Hydrogenation generally refers to a chemical reaction involving the addition of hydrogen, and the process is often used to reduce or saturate organic materials.
- dehydrogenation The reverse reaction in which hydrogen is removed from an organic molecule is referred to as dehydrogenation.
- the use of hydrogenation and/or dehydrogenation catalysts has been found to be useful for transamination and reductive amination in the practice of the present invention.
- a wide variety of hydrogenation/dehydrogenation catalysts are known. Platinum group metals, particularly platinum, palladium, rhodium, and ruthenium form highly active hydrogenation/dehydrogenation catalysts. These are known to operate at lower temperatures and lower pressures of H 2 . Non-precious metal catalysts, especially those based on nickel (such as Raney nickel and Urushibara nickel) have also been developed as economical alternatives. Other hydrogenation/dehydrogenaton catalysts might incorporate iron, copper, chromium, molybdenum, cobalt, osmium, iridium, and/or the like. This invention requires the use of a catalyst comprising at least Ni or Ni and Re.
- the catalyst material incorporates hydrogenation/dehydrogenation catalytic ingredients comprising nickel and rhenium.
- the weight ratio of nickel to rhenium may vary over a wide range.
- the weight ratio of nickel to rhenium may be in the range from 1:1000 to 1000:1, preferably 1:100 to 100:1, more preferably 1:50 to 50:1.
- the weight ratio of nickel to rhenium is within these ranges with the proviso that the weight ratio is also greater than 1:1.
- using a weight ratio from 3:1 to 10:1 would be suitable.
- a useful support are alumina-silicate particles.
- heterogeneous catalysts are preferred. Often, heterogeneous catalysts comprise one or more catalytic materials supported upon a suitable substrate.
- the substrate may be used in various shapes or combinations such as, for example, powder, particle, pellet, granule, extrudate, fiber, shell, honeycomb, plate, or the like.
- the particles can be regular in shape, irregular, dendritic, dendrite-free, or the like.
- Preferred supports are particulate in nature or powders.
- Particulate support may have a so-called guest/host structure which may be prepared by adsorbing or adhering fine (less than 100 micrometers, preferably less than 50 micrometers and most preferably less than 10 micrometer in size) nanoporous particles on coarser (greater than 30 mesh) particles.
- the smaller particles are referred to as guests, while the large particles supporting them are referred to as hosts.
- This small-particle-supported-on-a-larger-particle composite structure provides very high total exterior surface area while retaining the desirable gas passing characteristics, i.e., low pressure drop, of a coarser particle.
- inexpensive, coarser particles can be used.
- very inexpensive, highly active catalyst particles can be prepared since the bulk of the volume of a catalyst bed may be taken up by the inexpensive, underlying, coarser particles.
- the catalyst material can be incorporated into or onto the guest and/or host particles. Often, the catalyst material is incorporated mainly onto the guest material before or after the guest/host composite is formed. Guest/host structures and methods of making these are further described in U.S. Publication No. 2005-0095189 A1 .
- the catalyst and/or the supported catalyst composition is calcined prior to use.
- calcining can occur in air or an inert atmosphere such as one based upon nitrogen, argon, carbon dioxide, combinations of these, and the like.
- Calcining can occur at a variety of elevated temperatures, such as a temperature up to 1000°C, preferably 200°C to 800°C.
- a wide variety of materials may serve as suitable supports in the practice of the present invention.
- Representative examples include carbonaceous materials, silicaceous materials (such as silica), metal compounds such as metal oxides, combinations of these, and the like.
- Representative metal oxides include oxides of one or more of magnesium, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, iron, tin, antimony, barium, lanthanum, hafnium, thallium, tungsten, rhenium, osmium, iridium, and platinum.
- carbonaceous substances include activated carbon and graphite.
- Suitable activated carbon particles may be derived from a wide variety of source(s) including coal, coconut, peat, any activated carbon(s) from any source(s), combinations of at least two of these, and/or the like.
- Catalyst material may be incorporated into heterogeneous catalyst systems in a variety of ways.
- a catalyst precursor is first provided on the support, and then the precursor can be converted into the catalyst itself afterward.
- Exemplary procedures are well known in the industry and include solution impregnation, precipitation, vapor deposition such as by PVD or CVD techniques, and the like.
- the amount of catalyst used in forming a cyclic triamine using transamination strategies is any amount which is effective in producing the desire cyclic triamine.
- the quantity of catalyst may be in the range from 0.1 to 20 weight percent, preferably 1 to 15 weight percent, of catalyst per 100 parts by weight of reactant(s) to be self-cyclized to form the desired triamine.
- a typical strategy might involve causing a flow of reactants to contact a bed of heterogeneous catalyst particles.
- the space velocity (usually expressed in units of gmol/(kg catalyst/hr) can be adjusted to balance factors such as production and selectivity.
- the weight percent of catalyst when calculating the weight percent of catalyst for batch or continuous processes, only the actual amount of active catalytic substance is used to determine the weight percent of catalyst.
- 100 parts by weight of heterogeneous catalyst particles might be used to treat a mixture containing 91 parts by weight of L-TETA and 9 parts by weight of TAEA. Other amines may or may not be present in the mix.
- the total amount of reactants is 100 parts by weight.
- the heterogenous catalyst particles might include 5 part by weight ofNi and 1 part by weight of Re as metals for a total of 6 parts by weight of catalyst.
- the batch reactor would include 6 parts by weight of the catalyst per 100 parts by weight of the reactants.
- the catalyst is present as a molecule such as an oxide or the like, only the weight of the active metal catalyst constituent is used to determine the weight percent.
- the reactant mixture for transamination optionally, may include hydrogen. When hydrogen is used, the level of hydrogen can be adjusted to favor ring closure. Generally, a lower hydrogen concentration favors ring closure. From 0 to 50 mole percent, desirably 0.1 to 25 mole percent of hydrogen per mole of reactants would be suitable.
- the reactant mixture for transamination optionally may include ammonia. Ammonia can help suppress the production of undesired by-products. Ammonia can be a reactant in transamination. From 0 to about 100 mole percent, desirably 1 to 25 mole percent of ammonia per mole of reactants would be suitable.
- the reaction mixture optionally may include one or more additional amines.
- Such amines are not considered amines hereunder.
- Such other amines are present as a practical matter, for instance, when the feed used in the processes of the present invention is obtained as the output of an industrial process.
- the present invention can be used to process this output to increase the cyclic triamine content.
- the output can be used as is as a feed herein or can be processed first, as desired, such as to remove one or more constituents prior to enrichment.
- an output of an industrial process may be a mixture including one or more amines including at least one tetramine, desirably at least one of L-TETA and TAEA if transamination techniques are used.
- Such mixture might even include a desired cyclic triamine such as some AEP.
- a mixture can be used as a reactant mixture in the practice of the invention to enrich the cyclic triamine content.
- an illustrative output of an industrial process might include ethylenediamine (EDA), piperazine (PIP), diethylenetriamine (DETA), AEP, L-TETA, N-(Piperazinoethyl)ethylenediamine (PEEDA), Tetraethylenepentamine (L-TEPA), and others.
- This mixture can be processed in the practice of the present invention to increase the AEP content.
- one or more of the amines of such a starting mixture, including the AEP can be removed prior to being subjected to the transamination reaction. Examples of enriching the AEP content of such a mixture and other mixtures in the context of both transamination and reductive amination are provided below.
- Some of the amine constituents of such a mixture can react to make higher amines. These higher amines can ring close to yield a cyclic triamine such as AEP and a by-product such as ammonia or an amine.
- the reaction mixture for transamination can be contacted with catalyst at temperatures of from 130°C to 170°C for transamination. Below the preferred temperature ranges, the conversion to cyclic triamine may be too slow to be practical for commercial scale production. Above the preferred temperature ranges, selectivity may be reduced to an undue degree, increasing the yield of by-products. In some instances, such by-products may have commercial value and be desirable as a consequence. In other instances, by-products constitute impurities as a practical matter.
- the reaction mixture for transamination is contacted with catalyst at pressure(s) in the range of 400 psi (2,758 kPa) to 800 psi (5,516 kPa).
- the pressure is sufficient to maintain the reactor contents in a liquid state as the reaction proceeds.
- the pressure will vary as the reaction proceeds.
- ammonia is a by-product of a typical transamination process. The production of ammonia causes the pressure generally to increase as the reaction proceeds. Ammonia and/or other pressure-increasing products can be removed from the reactor in order to keep the pressure below a desired threshold.
- precursors can be converted into suitable starting materials, which are then converted to cyclic triamines via transamination reactions.
- an amine or a mixture of amines can be alkoxylated to form starting materials.
- a stream containing EDA and DETA can be ethoxylated to give a mixture including symmetrical and/or unsymmetrical DiHEED and linear and/or branched hydroxyethyl DETA.
- These product intermediates can be converted to cyclic triamines as described herein using transamination techniques.
- a catalyst was prepared by an incipient wetness technique using two impregnations.
- a solution of 107.6 grams of nickel nitrate hexahydrate (Aldrich no. 244074; crystal, 98%) and 8.26 grams of ammonium perrhenate (Molymet) in 318 ml deionized water was prepared.
- a second impregnation using the remaining solution (188 ml) was followed by calcination at 340°C for 3 hours.
- the catalyst was reduced at 340°C in flowing hydrogen at a flow rate of ⁇ 1600 cc/min for three hours. Following the reduction, the catalyst was allowed to cool to room temperature and passivated using 1% oxygen in nitrogen to allow handling in air.
- the final yield was 325.5 grams of catalyst with a nominal composition of 6.8 wt. % nickel and 1.8 wt. % rhenium on alumina-silica.
- the catalyst was used to convert L-TETA to AEP.
- the L-TETA was supplied in a reaction mixture including other amines per Table A. Seven runs were performed at different, respective temperatures ranging from 120°C to 155°C. Each reaction took place over 295 grams of catalyst described above loaded into 86.25" of 0.688" ID stainless steel tubing. A temperature traverse from 120-155°C was conducted with an amine feed rate of 500 ⁇ 1000 gmole/hr/kg-cat - , and H2 flow at 9-10 slph (about 10x hydrogen necessary to saturate the feed). All testing was done at 800 psig.
- Table 1 gives the results from reacting 900 grams of EDA with 100 grams of a Ni/Re catalyst at 160 C and an initial hydrogen pressure of 100 psig.
- the pressure of the reactor during the run was 170 to 730 psig.
- AEP increases with EDA conversion, but still represents only a small portion ( ⁇ 5 percent) of the product mix even at high EDA conversion.
- the amount of AEP in the product mix was enriched by almost 300% relative to the reactant mixture. On an industrial scale, depending on the size of the commercial unit, this can result in a significant amount of extra pounds of AEP on an annual basis.
- Table 2 gives the results from reacting 844 grams of EDA with 100 grams of a commercial nickel on silica/alumina catalyst at 145-158°C and an initial hydrogen pressure of 270 psig but otherwise using the procedures of Example 2.
- the pressure of the reactor during the run was 800 to 1135 psig.
- AEP increases with EDA conversion. These conditions produced less AEP at a given EDA conversion than those in Table 1 above.
- Table 3 gives the results from reacting 740 grams of EDA with 100 grams of a commercial nickel on silica catalyst at 160-185°C and an initial hydrogen pressure of 236 psig but otherwise using the procedures of Example 2.
- the pressure of the reactor during the run was 960 to 2140 psig.
- AEP increases with EDA conversion. These conditions produced more AEP at a given EDA conversion than those in Table 2, but less than the process conditions for Table 1.
- Table 4 gives the results from reacting 800 grams of EDA with 100 grams of a commercial nickel on silica catalyst at 179-180°.C and an initial hydrogen pressure of 40 psig but otherwise using the procedures of Example 2.
- the pressure of the reactor during the run was 650 to 1000 psig.
- AEP increases with EDA conversion. Comparing these results with Table 3 which uses the same catalyst, shows these conditions at an initial lower hydrogen concentration produced more AEP at a given EDA conversion than process conditions for Table 3.
- Table 5 gives the results from reacting 802 grams of a mixed EDA/DETA with 100 grams of a Ni/Re on alumina/silica (80:20) catalyst at 150-155°C at an initial hydrogen pressure of 150 psig but otherwise using the procedures of Example 2.
- the pressure of the reactor during the run was 215 to 670 psig.
- AEP increases with EDA conversion. Comparing these results with Tables 1-4 above shows this feed does not produce a significant increase in AEP in the final product mix
- Example 2 to 5 suggests adding more DETA would give more AEP. As shown here, starting with more DETA at the outset does not lead to significantly more production of AEP. It is believed that the DETA is converted to PIP, which essentially stops further reactions as a practical matter. This shows that using even higher amines having 4 or more amines per molecule as described in further examples provides a much more effective route to cyclic amines such as AEP. It is believed that these further routes are more effective because they proceed via ring closure and/or reduction mechanisms that proceed substantially through alternative immediates rather than PIP.
- Table 6 gives the results from reacting 800 grams of a mixed ethyleneamines feed which has a large percentage of linear TETA in the mix, with 100 grams of a commercial nickel on silica catalyst at 150-155°C in the absence of hydrogen but otherwise using the procedures of Example 2.
- the pressure of the reactor during the run was 286 to 730 psig.
- AEP increases with feed conversion. Comparing these results with Tables 1-5 shows this feed produces a much more significant amount of AEP in the final product mix compared to when EDA or a mix of EDA/DETA is used as the feed.
- This example uses a commercially available TETA obtained from an EDC process.
- Table 7 shows the composition of the commercial product and gives the results from reacting 800 grams of the mixed ethyleneamines feed, which has a large percentage of linear TETA in the mix, with 100 grams of a commercial nickel on silica catalyst at 150°C and an initial hydrogen pressure of 36 psig but otherwise using the procedures of Example 2.
- the pressure of the reactor during the run was 186 to 613 psig.
- AEP increases with feed conversion. Comparing these results with Tables 1-5 shows this feed produces a much more significant amount of AEP in the final product mix compared to when EDA or EDA/DETA is used as the feed.
- Table 8 gives the results from reacting 800 grams of TAEA, with 100 grams of a commercial nickel on silica catalyst at 150°C in the absence of hydrogen but otherwise using the procedures of Example 2.
- the pressure of the reactor during the run was 213 to 730 psig.
- AEP increases with TAEA conversion. Comparing these results with Tables 1-7 show that TAEA produces significantly more AEP in the final product mix compared to when EDA, EDA/DETA, or feeds which have a high percentage of linear TETA is used as the feed.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Catalysts (AREA)
Description
- The present non-provisional patent Application claims benefit from United States Provisional Patent Application having serial number
61/195,412, filed on October 6, 2008, by Stephen W. King - The present invention relates to processes for making cyclic triamines using transamination techniques. The cyclic triamines are made from higher amine precursors via ring closure reactions in the presence of a suitable catalyst.
- Cyclic triamines such as aminoethylpiperazine ("AEP,") have many industrial uses. For instance, these compounds are useful as dispersants, epoxy curing agents, chelants, catalysts, accelerators, hardeners, extenders in polymer fabrication, starting materials in the preparation of other amines, starting materials for making pesticides, and the like. AEP is also known by other names including 2-piperazin-1-ylethaneamine; 2-(1-piperazinyl) ethylamine; N-AEP, N-(2-aminoethyl) piperazine; 2-piperazinoethylamine; 1-(2-aminoethyl)piperazine, 1-piperazine ethaneamine, and 1-aminoethylpiperazine.
- A variety of processes for making cyclic triamines are known. According to one approach, AEP is a by-product formed from the reaction of ethylenedichloride (EDC) and ammonia or amines to form higher amines. See, e.g., Russian Patent Documents
2226188 2186761 - Cyclic triamines can also be formed by reacting hydroxyl functional reactants (e.g., monoethanolamine or ethylene glycol) and/or amines with other amines or ammonia in the presence of acid catalysts at high temperatures, e.g., 300°C or higher. Acid catalysts include, for example, phosphorous doped, niobium doped, or tungsten doped metal oxides and several mixed metal oxides including zeolites. For example,
US 5256786 uses a magnesium silicate catalyst with piperazine (PIP) and ethylenediamine (EDA) as feed to produce AEP at 53% selectivity at 9% conversion.US 5073635 shows examples of monoethanolamine (MEA) and PIP (1/1 mole ratio) with other metal silicates (Y, La, Ce, Nb, Zr, Ti) with conversions of ∼20-40% and AEP selectivities of 70-84%. -
US 4983735 claims heteropolytungstates for the MEA + PIP reaction. Fixed bed results show up to 68% conversion of PIP with about 65% selectivity to aminoethylpiperazine (AEP). -
US 5030740 teaches the use of tungsten oxide/titania for conversion of crude piperazine and MEA to AEP. Here selectivity to AEP is lower in part due to the high MEA/PIP ratio of 1:3, the relatively high conversion of MEA, and the reaction of EDA and diethylenetriamine (DETA) with MEA. -
US 4927931 has examples based on niobium oxide and niobium phosphate catalysts. Selectivity is lower than with the silicates. - Journal of Catalysis, 144(2), 556-68; 1993 discloses using a H+-pentasil zeolite (Si/Al = 25-19,000) at 350 C, a LHSV approximately 0.8 h-1, atm. pressure in a plug flow reactor. Ethylenediamine and its linear and cyclic oligomers result in piperazine and 1,4-diabicyclo(2.2.2)octane (TEDA), with small levels of AEP being formed.
-
US 5225599 discloses a process for the preparation of triethylenetetramine and N-(2-aminoethyl)ethanolamine . This process comprises the condensation of an alkyleneamine and an alkylene glycol in the presence of a condensation catalyst selected from Group IVB oxides or Group VIB compounds and a catalyst promoter. A mixture of silicotungstic acid (18 g), H2O, and TiO2/WO3 (55 g) was heated to 350 to give a catalyst. A mixture of ethylenediamine and ethylene glycol (2.95 mol ratio) was fed into a tube containing the above catalyst at 269.8 and 614.7 psig to give a product containing 6.13% by weight piperazine, 18.71 % by weight triethylenetetramine, 47.84% by weight N-(2-aminethyl)ethanolamine; and 2.39% by weight N-(2-aminoethyl)piperazine, and 24.93% by weight other products. -
US 4906782 discloses a process whereby alkyleneamines having an increased number of alkylene units are prepared by reacting NH3 and/or an alkyleneamine with an alkanolamine in the presence of a Nb-containing catalyst insoluble or slightly soluble in the aqueous reaction solution. Ethylenediamine 90, monoethanolamine 45, and NbO5 1.4 g were heated at 300 for 5 to give piperazine 2.3, diethylenetriamine 59.8, N-(2-aminoethyl)ethanolamine 2.6, N-(2-aminoethyl)piperazine 1.0, triethylenetetramine (isomers) 15.0, tetraethylenepentamine (isomers) 2.0, and pentaethylenehexamine (isomers) 1.0%, vs. 0.1, 76.0, 23.8, 0, 0, 0, 0, respectively, when using silica-alumina in place of NbO5. - In
US 4922024 amines (esp. acyclic polyalkylenepolyamines) are prepared by amination of alcohols with reactant amines in the presence of H2 and binary or ternary compounds of Group VIB metals as catalysts. Thus, 50 mL of a mixture of diethylenetriamine (I) and H2NCH2CH2OH (II) (mole ratio 2:1) was autoclaved over 6.3 g WB-WB2 catalyst at 315 and 365 psig H2 for 5.0 h to show 36% conversion of 11 and the following selectivities (I-and II-free basis): H2NCH2CH2NH2 19, triethylenetetramine 27, tetraethylenepentamine 36, piperazine 7, N-(2-aminoethyl)piperazine 9, and N-(2-aminoethyl)ethanolamine 1%. -
US 4806517 shows that linear polyethylenepolyamines are prepared by the condensation of ethylenediamine (I) with ethanolamine (II) over a catalyst which is prepared by impregnating Group IVB element oxide pellets with an aqueous solution of a P-O compd. at 20-150°C so as to bond 0.5-6% of the P to the surface of the pellets in the form of hydroxy-containing phosphate groups, and then calcining at 200-900. A 100 mL solution of 85% H3PO4 was heated to 130°C under an inert atmosphere,105 cm3 of TiO2 pellets were added, the mixture reacted for 2 h, and calcined at 600°C for 16 h. The catalyst was contacted with a 2:1 molar ratio I-II mixt. of 325, producing approximately 65% II conversion with the formation (selectivity %) of piperazine 1.8, diothylenetriamine 59.0, N-(2-aminoethyl)ethanolamine 0.7, N-(2-aminoethyl)piperazine and N-(hydroxyethylpiperazine 2.1, triethylenetetramine 19.6, and tetraethylenepentamine 4.2%. -
US 4584405 Polyethylenepolyamines are prepared with high selectivity to linear products, from ethylenediamine (I) and ethanolamine (II) using activated C catalysts (optionally pretreated with strong mineral acids). -
US 4552961 Predominantly linearly extended polyalkylene polyamines are produced by treating alkylenediamines with alkylene glycols or alkanolamines using a P amide catalyst. - Other strategies use reductive amination methods in which alkanolamines are reacted with ammonia and/or alkyleneamines to produce cyclic triamines. Generally, only a small amount, e.g., less than 10 percent, of AEP is contained in the final product mixture. Examples of this practice using hydrogenation catalysts are described in
U.S. Pat. Nos. 5455352 ;5248827 ; and4602091 . - It remains desirable to develop strategies for making cyclic triamines with improved conversion and selectivity. It would also be desirable if the reaction conditions could be moderate in terms of temperature, and have improved catalyst stability.
- The present invention provides strategies for making cyclic triamines. It has been discovered that reactant media including certain precursors and/or certain types of catalysts can be converted into cyclic triamines with improved conversion and selectivity. The strategies can be incorporated into reactions that involve transamination mechanisms. In the case of transamination, for instance, using transamination to self-cyclize higher amines of the type including at least four amine moieties in the presence of a suitable catalyst leads to desired cyclic triamines with notable conversion and yield. Preferred embodiments can produce reaction mixtures that are generally free of salt by-products.
- In one aspect, the present invention relates to a method of making a cyclic triamine of the type comprising first and second nitrogen backbone atoms and an N-amino moiety pendant from at least one of.the nitrogen backbone atoms, comprising the steps of:
- a) providing a polyfunctional compound comprising at least 4 amine moieties, and, optionally, one or more nitrile moieties;
- b) causing ring closure of the polyfunctional compound in the presence of a catalyst comprising at least Ni or Ni and Re at a temperature of from 130°C to 170°C and a pressure in the range of 400 psi (2,758 kPa) to 800 psi (5,516 kPa), to cause the polyfunctional compound to react with itself to form the cyclic triamine.
- In another aspect, the present invention relates to a method of making a cyclic triamine of the type comprising first and second nitrogen backbone atoms and an N-amino moiety pendant from at least one of the nitrogen backbone atoms, comprising the steps of:
- a) providing a tetraamine; and
- b) causing the ring closure of the tetraamine in the presence of a catalyst comprising at least Ni or Ni and Re at a temperature of from 130°C to 170°C and a pressure in the range of 400 psi (2,758 kPa) to 800 psi (5,516 kPa), to cause the tetraamine to react with itself to form the cyclic triamine.
-
-
Fig. 1 shows a general formula for cyclic triamine. -
Fig. 2 shows a general formula for a cyclic triamine that incorporates a piperazine moiety. -
Fig. 3 shows a triamine that incorporates a piperazine moiety. -
Fig. 4 shows an aminoethylpiperazine. -
Fig. 5 shows a general formula for a linear higher amine. -
Fig. 6 shows a general formula for a linear tetraamine. -
Fig. 7 shows the formula for linear triethyltetramine. -
Fig. 8 shows a general formula for a branched higher amine. -
Fig. 9 shows a general formula for a branched higher amine. -
Fig. 10 shows a specific linear tetramine. - Reference will now be made in detail to representative embodiments of the invention. While the invention will be described in conjunction with the enumerated embodiments, it will be understood that they are not intended to limit the invention to those embodiments. On the contrary, the invention is intended to cover all alternatives, modifications, and equivalents that may be included within the scope of the present invention as defined by the claims.
- One skilled in the art will recognize many methods and materials similar or equivalent to those described herein, which could be used in and are within the scope of the practice of the present invention. The present invention is in no way limited to the methods and materials described.
- The publications discussed above and throughout the text are provided solely for their disclosure prior to the filing date of the present application. Nothing herein is to be construed as an admission that the inventor is not entitled to antedate such disclosure by virtue of prior invention.
- Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. Although any methods, devices, and materials similar or equivalent to those described herein can be used in the practice or testing of the invention, the preferred methods, devices and materials are now described.
- The present invention provides a strategy for making cyclic triamines of the type comprising first and second nitrogen backbone atoms and an N-amino moiety pendant from at least one of the nitrogen backbone atoms. The amine groups of the triamine can be primary, secondary, tertiary, or a combination of these. The cyclic triamine can be fully saturated or may include double bonds in the backbone of the cyclic moiety and/or in a moiety pendant from the cyclic moiety. Cyclic triamines may be substituted or non-substituted. As used herein "substituted" means that a moiety other than H is pendant to the backbone. "Non-substituted" means that, other than the N-amino moiety(ies), other substituents of the backbone are hydrogen.
- In representative embodiments, cyclic triamines of the present invention are represented by the formula shown in
Fig. 1 , wherein each of R1, R5, and R6 is independently a monovalent moiety or co-member of a ring structure but do not include N as a constituent of an amine moiety. Any of R1, R5, and R6 may optionally include one or more heteroatoms other than N in the backbone or a moiety pendant from the backbone. Examples of moieties suitable as R1, R3, and R6 include but are not limited to H; linear, branched, or cyclic hydrocarbyl such as alkyl, aryl, aralkyl, or the like; a monovalent moiety including one or more heteroatoms; polyether chains comprising one or more oxyalkylene repeating units such as -R17O-, wherein R17 is often alkylene of 2 to 5 carbon atoms; other oligomeric or polymer chains of at least 2 repeating units; -R18N- wherein R18 is alkylene of at least 2, preferably 2 to 5 carbon atoms. Preferably, each of R1, R5, and R6 independently is H or straight, branched, or cyclic hydrocarbyl such as alkyl of 1 to 10 carbon atoms, preferably 1 to 3 carbon atoms. More preferably, each of R1, R5, and R6 is H. - Each of R2, R3, and R4 is independently any suitable divalent moiety that may be substituted or unsubstituted. Examples of suitable divalent moieties include linear, branched, or cyclic hydrocarbylene moieties such as alkylene, arylene, aralkylene, or the like; polyether chains comprising one or more oxyalkylene repeating units such as -R17-, wherein R17 is often alkylene of 2 to 5 carbon atoms; other oligomeric or polymer chains of at least 2 repeating units; and/or -R18N- wherein R18 is alkylene of at least 2, preferably 2 to 5 carbon atoms. Preferably, each of R2, R3, and R4 is independently an alkylene moiety of 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms, often ethylene.
- If any of R1, R2, R3, R4, R5, or R6 includes functional groups, these may be masked in accordance with conventional masking strategies to protect them in the course of the reaction described herein. After the reaction is completed, the functional groups can be unmasked if desired.
- In preferred embodiments, the cyclic moiety incorporated into the cyclic triamine is a six-membered ring in which the two nitrogen backbone atoms are at positions 1 and 4 relative to each other in the ring and each nitrogen respectively constitutes a portion of an amine moiety. The other 4 atoms in the ring are carbon atoms. Further, an N-amino moiety is linked to at least one of these backbone nitrogens. Such a six-membered ring will be referred to herein as a piperazine moiety. In representative embodiments, a cyclic triamine incorporating a piperazine moiety has the formula shown in
Fig. 2 , wherein R1, R4, R5, and R6 are as defined above and each of R7 through R14 is independently a monovalent moiety or a co-member of a ring structure. Preferably, each of R7 and R14 is independently a monovalent moiety according to the definitions of R1, R5, and R6. More preferably, each of R7 through R14 are hydrogen such that the cyclic amine has the formula shown inFig. 3 . - In a particularly preferred mode of practice, the cyclic triamine is aminoethylpiperazine of the formula shown in
Fig. 4 . This compound is commonly referred to as "AEP" and is unique for including a primary, secondary, and tertiary amine. AEP has many uses that include inhibition of corrosion, epoxy curing, surface activating, constituent of asphalt adhesive, mineral processing aid, and the like. AEP is also known by other names, including 2-piperazin-1-ylethaneamine; 2-(1-piperazinyl) ethylamine; N-AEP, N-(2-aminoethyl) piperazine; 2-piperazinoethylamine; 1-(2-aminoethyl)piperazine, 1-piperazine ethaneamine, and 1-aminoethylpiperazine. - In the practice of the present invention, cyclic triamines are formed by reacting one or more suitable precursors under conditions effective to achieve the desired product. Transamination techniques are used to convert amines having four or more amine moieties (hereinafter "higher amines") into the desired cyclic triamine. Transamination techniques are used to form cyclic triamines from a wide range of precursors in the presence of a catalyst comprising Ni and Re.
- The methods of the present invention are selective for the desired product at high conversion of the precursor and selectivity for the desired product. For purposes of this invention, "conversion" refers to the total weight percentage of reactant lost as a result of reactions. The conversion can vary depending upon factors such as the reactants, catalyst, process conditions, and the like. In many embodiments, the conversion is at least 2 weight percent, preferably at least 10 weight percent, more preferably at least 25 weight percent, most preferably at least 35 weight percent.
- For purposes of the invention, "selectivity" refers to the weight percentage of converted reactant(s) that form a desired cyclic triamine. Like conversion, selectivity will vary based upon factors including the reactants, catalyst, process conditions, and the like. In the practice of the present invention, selectivity for forming cyclic triamine in more preferred embodiments is at least 10%, preferably at least 25%, more preferably at least 50%.
- In preferred modes, the reaction occurs at moderate temperature with a moderate resultant impurity load. Many leftover reactants, if any, and by-products, if any, have commercial value independent of the desired cyclic triamine product. After removing the desired product(s) from such mixtures, the remaining product mixture has many uses, including being recycled as a feed for the cyclization reaction, refined to recover some of the product(s) in more pure form, used as reactants in other reactions, used as is or with any desired modification as products such as epoxy curing agents, combinations of these, and the like.
- The methods of the invention can be practiced in any suitable reactor. These include batch reactors, continuous fixed bed reactors, slurry bed reactors, fluidized bed reactors, catalytic distillation reactors, combinations of these, and the like.
- According to one desirable methodology of the present invention for forming cyclic triamines, a higher amine is self-cyclized to from the cyclic triamine in the presence of a suitable catalyst via transamination techniques. Transamination generally refers to the transfer of one amine from one location to another. When two different reactants are subjected to a transamination reaction, an amine moiety is transferred from one molecule to the other. When a molecule is self-cyclized by reacting with itself, there is a transposition of an amino group within the molecule. Schematically, the reaction can be viewed as causing one of the amine moieties to be removed from the molecule, allowing the other amine to bond to the location vacated by the removed amine group.
- The polyfunctional compounds used in the transamination reaction of the present invention can include a combination of primary, secondary, and tertiary amine moieties, but it is desirable if at least two of the amine moieties are primary and/or secondary to facilitate self-cyclization. Reactants can include a combination of one or more of such higher amines. The higher amine in many embodiments is linear or branched. For instance, in exemplary embodiments, a representative class of linear higher amines may be represented by the general formula of the following class of tetraamines shown in
Fig. 5 , wherein each of R2, R3, R4, R5, and R6 is independently as defined above, and each of R15 and R16 is independently a monovalent moiety according to the definitions for R1, R5, and R6 above. In preferred embodiments, a linear tetraamine has the formula shown inFig. 6 , wherein each of R2 R3, and R4 is each independently as defined above. - In a more preferred embodiment, a linear tetraamine has the formula shown in
Fig. 7 . This compound is known as linear triethylenetetraamine or L-TETA. - In other exemplary embodiments, a representative class of branched higher amines may be represented by the general formula of the following class of tetraamines shown in
Fig. 8 , wherein each of R2, R3, R4, R5, and R6 is independently as defined above, and R17 is a monovalent moiety according to the definitions for R1, R5, and R6 above. In preferred embodiments, a branched tetraamine has the formula shown inFig. 9 , wherein each of R2, R3, and R4 is each independently as defined above. - In a more preferred embodiment, a linear tetraamine has the formula shown in
Fig.10 . This compound is known as trisaminoethylamine (TAEA). Other examples of higher amines include pentaamines such as tetraethylenepentaamine (TEPA), pentaethylenehexamine (PEHA), and other higher ethyleneamines generally referred to as heavy polyethyleneamines (HPA), combinations of these, and the like. Higher amines with cyclic moieties that can be cracked back to a cyclic triamine such as AEP also may be used. - Mixtures of higher amines can also be used. For instance, a suitable reaction medium might include a combination of L-TETA and TAEA wherein the weight ration of L-TETA to TAEA is in the range from 1:1000 to 1000:1, preferably 1:50 to 50:1, or even 1:5 to 5:1. While the above identified classes of higher amines and specific examples thereof are representative of those useful in the practice of the present invention, one or more other higher amines could be used as well, including those that are monomeric, oligomeric, or polymeric. As used herein, an oligomer refers to a compound incorporating 2 to 10 monomeric residues. A polymer refers to a compound incorporating more than 10 monomeric residues.
- In an exemplary transamination reaction scheme, a reaction medium comprising one or more higher amine reactants is self cyclized. For instance, L-TETA and/or TAEA can be self-cyclized to produce AEP with ammonia as a by-product. Alternatively, a pentaamine such as TEPA can be self-cyclized to produce AEP with ethylenediamine (EDA) as a by-product.
- The higher amine reactant(s) used in the self-cyclizing reaction can be supplied in substantially pure form or can be present with other ingredients, including other amines. For example, an output of an exemplary industrial process may be a mixture including one or more amines including at least one higher amine, desirably at least one of L-TETA and/or TAEA. Such mixture might even include a desired cyclic triamine such as some AEP. Such a mixture can be used as a reactant mixture in the practice of the invention. The product mixture will be enriched with cyclic triamine content relative to the starting reaction medium.
- As just one example, an illustrative output of an industrial process might include ethylenediamine (EDA), piperazine (PIP), diethylenetriamine (DETA), AEP, L-TETA, N-(Piperazinoethyl)ethylenediamine (PEEDA), Tetraethylenepentamine (L-TEPA), and others. This mixture can be processed in the practice of the present invention to increase the AEP content. Optionally, one or more of the amines of such a starting mixture, including the AEP, can be removed prior to being subjected to the transamination reaction. Examples of enriching the AEP content of such a mixture and other mixtures as well are provided below.
- Nitrile functional amine precursors can also be used in the transamination methodologies. In the course of the transamination, the nitrile groups can react with amines to give cyclic compounds, or may be converted to imines which can react with amines to give cyclic compounds or be reduced to the amine which can then proceed to cyclize via transamination.
- In many embodiments, the amine mixture used as a starting reaction material for transamination will be in liquid form such that no additional solvent is needed. Indeed, in many instances it may be preferred to carry out the desired reaction in the absence of solvent. However, one or more solvents may be used if desired. A variety of solvents or combinations of solvents may be used. Desirably, the solvent is not unduly reactive with the higher amine reactant(s) or cyclic triamine product(s) and does not unduly decompose under the reaction conditions. Some examples of solvents that could be used include saturated hydrocarbons such as pentane, hexane, octane, nonane, decane, or the like; aromatic hydrocarbons such as toluene, benzene, xylene, esther, combinations of these, and the like. Alcohols are desirably avoided, as many of these are capable of reacting with the amine reactants and/or products. If present, the amount of solvent used may vary over a wide range. In a typical instance, the solvent may constitute from 5 to 98 weight percent, desirably 10 to 80 weight percent, of the mixture. Optionally when solvent is used, the reaction medium can be diluted to favor intramolecular reactions and, hence, cyclization, relative to intermolecular interactions.
- A variety of catalysts comprising at least one of Ni and Re can be used in the practice of the present invention for transamination. Catalysts can be acidic, alkaline, neutral, or a combination of different catalysts can be used. Representative classes of catalyst metals, alloys, intermetallic compositions, or molecules (such as oxides, nitrides, phosphates, silicates, and the like, or mixtures of one or more transition metals, including the lanthanoid and/or actinoid series. A wide variety of catalysts applicable to amine chemistry are described in
U.S. Pat. Nos. 6,534,441 ;5,256,786 ;5,073,635 ;4,983,735 ;5,030,740 ;4,927,931 ;5,222,599 ;4,906,782 ;4,922,024 ;4,806,517 ;4,584,405 ;4,552,961 ;5,455,352 ;5,248,827 ;4,602,091 . See also Russian patents2226188 2186761 - In a preferred embodiment, the catalyst incorporates one or more hydrogenation and/or dehydrogenation catalysts. Hydrogenation generally refers to a chemical reaction involving the addition of hydrogen, and the process is often used to reduce or saturate organic materials. The reverse reaction in which hydrogen is removed from an organic molecule is referred to as dehydrogenation. The use of hydrogenation and/or dehydrogenation catalysts has been found to be useful for transamination and reductive amination in the practice of the present invention.
- A wide variety of hydrogenation/dehydrogenation catalysts are known. Platinum group metals, particularly platinum, palladium, rhodium, and ruthenium form highly active hydrogenation/dehydrogenation catalysts. These are known to operate at lower temperatures and lower pressures of H2. Non-precious metal catalysts, especially those based on nickel (such as Raney nickel and Urushibara nickel) have also been developed as economical alternatives. Other hydrogenation/dehydrogenaton catalysts might incorporate iron, copper, chromium, molybdenum, cobalt, osmium, iridium, and/or the like. This invention requires the use of a catalyst comprising at least Ni or Ni and Re.
- In particularly preferred embodiments, the catalyst material incorporates hydrogenation/dehydrogenation catalytic ingredients comprising nickel and rhenium. The weight ratio of nickel to rhenium may vary over a wide range. For instance, the weight ratio of nickel to rhenium may be in the range from 1:1000 to 1000:1, preferably 1:100 to 100:1, more preferably 1:50 to 50:1. Even more desirably, the weight ratio of nickel to rhenium is within these ranges with the proviso that the weight ratio is also greater than 1:1. In illustrative embodiments, using a weight ratio from 3:1 to 10:1 would be suitable. In preferred embodiments in which a heterogeneous catalyst incorporates nickel and rhenium, a useful support are alumina-silicate particles. Such catalysts and methods of making such heterogeneous catalysts on such supports are further described in
U.S. Pat. No. 6,534,441 . Such catalysts are also further described in Assignee's co-pending U.S. Provisional Patent Application titled Attorney Docket Number 66049 (DOW0015/P1) titled "LOW METAL LOADED, ALUMINA SUPPORTED, CATALYST COMPOSITIONS AND AMINATION PROCESS" by Steven W. King et al. and filed co-currently with the present application. Additional suitable catalysts are also described in Assignee's co-pending U.S. Provisional Patent Application having Attorney Docket Number 67688 (DOW0016/P1) titled "LOW METAL CATALYST COMPOSITIONS INCLUDING ACIDIC MIXED METAL OXIDE AS SUPPORT" by Steven W. King et al. also filed co-currently herewith. - Heterogeneous catalysts are preferred. Often, heterogeneous catalysts comprise one or more catalytic materials supported upon a suitable substrate. The substrate may be used in various shapes or combinations such as, for example, powder, particle, pellet, granule, extrudate, fiber, shell, honeycomb, plate, or the like. The particles can be regular in shape, irregular, dendritic, dendrite-free, or the like. Preferred supports are particulate in nature or powders.
- Particulate support may have a so-called guest/host structure which may be prepared by adsorbing or adhering fine (less than 100 micrometers, preferably less than 50 micrometers and most preferably less than 10 micrometer in size) nanoporous particles on coarser (greater than 30 mesh) particles. The smaller particles are referred to as guests, while the large particles supporting them are referred to as hosts. This small-particle-supported-on-a-larger-particle composite structure provides very high total exterior surface area while retaining the desirable gas passing characteristics, i.e., low pressure drop, of a coarser particle. In addition, by using smaller particles in constructing these composite particles, inexpensive, coarser particles can be used. Thus, very inexpensive, highly active catalyst particles can be prepared since the bulk of the volume of a catalyst bed may be taken up by the inexpensive, underlying, coarser particles.
- The catalyst material can be incorporated into or onto the guest and/or host particles. Often, the catalyst material is incorporated mainly onto the guest material before or after the guest/host composite is formed. Guest/host structures and methods of making these are further described in
U.S. Publication No. 2005-0095189 A1 . - Preferably, the catalyst and/or the supported catalyst composition is calcined prior to use. Generally, calcining can occur in air or an inert atmosphere such as one based upon nitrogen, argon, carbon dioxide, combinations of these, and the like. Calcining can occur at a variety of elevated temperatures, such as a temperature up to 1000°C, preferably 200°C to 800°C.
- A wide variety of materials may serve as suitable supports in the practice of the present invention. Representative examples include carbonaceous materials, silicaceous materials (such as silica), metal compounds such as metal oxides, combinations of these, and the like. Representative metal oxides include oxides of one or more of magnesium, aluminum, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, germanium, strontium, yttrium, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, indium, iron, tin, antimony, barium, lanthanum, hafnium, thallium, tungsten, rhenium, osmium, iridium, and platinum.
- Examples of carbonaceous substances include activated carbon and graphite. Suitable activated carbon particles may be derived from a wide variety of source(s) including coal, coconut, peat, any activated carbon(s) from any source(s), combinations of at least two of these, and/or the like.
- Catalyst material may be incorporated into heterogeneous catalyst systems in a variety of ways. In some instances, a catalyst precursor is first provided on the support, and then the precursor can be converted into the catalyst itself afterward. Exemplary procedures are well known in the industry and include solution impregnation, precipitation, vapor deposition such as by PVD or CVD techniques, and the like.
- The amount of catalyst used in forming a cyclic triamine using transamination strategies is any amount which is effective in producing the desire cyclic triamine. For batch conditions, the quantity of catalyst may be in the range from 0.1 to 20 weight percent, preferably 1 to 15 weight percent, of catalyst per 100 parts by weight of reactant(s) to be self-cyclized to form the desired triamine. In a continuous process, a typical strategy might involve causing a flow of reactants to contact a bed of heterogeneous catalyst particles. In such a case, the space velocity (usually expressed in units of gmol/(kg catalyst/hr) can be adjusted to balance factors such as production and selectivity.
- When calculating the weight percent of catalyst for batch or continuous processes, only the actual amount of active catalytic substance is used to determine the weight percent of catalyst. For instance, in an exemplary embodiment, 100 parts by weight of heterogeneous catalyst particles might be used to treat a mixture containing 91 parts by weight of L-TETA and 9 parts by weight of TAEA. Other amines may or may not be present in the mix. The total amount of reactants is 100 parts by weight. The heterogenous catalyst particles might include 5 part by weight ofNi and 1 part by weight of Re as metals for a total of 6 parts by weight of catalyst. In this case, the batch reactor would include 6 parts by weight of the catalyst per 100 parts by weight of the reactants. For purposes of the present invention, if the catalyst is present as a molecule such as an oxide or the like, only the weight of the active metal catalyst constituent is used to determine the weight percent.
- . The reactant mixture for transamination optionally, may include hydrogen. When hydrogen is used, the level of hydrogen can be adjusted to favor ring closure. Generally, a lower hydrogen concentration favors ring closure. From 0 to 50 mole percent, desirably 0.1 to 25 mole percent of hydrogen per mole of reactants would be suitable. The reactant mixture for transamination optionally may include ammonia. Ammonia can help suppress the production of undesired by-products. Ammonia can be a reactant in transamination. From 0 to about 100 mole percent, desirably 1 to 25 mole percent of ammonia per mole of reactants would be suitable. In addition to the desired reactant amine(s), the reaction mixture optionally may include one or more additional amines. If these are not reactive in a way to produce the desired cyclic triamine, such amines are not considered amines hereunder. Such other amines are present as a practical matter, for instance, when the feed used in the processes of the present invention is obtained as the output of an industrial process. The present invention can be used to process this output to increase the cyclic triamine content. The output can be used as is as a feed herein or can be processed first, as desired, such as to remove one or more constituents prior to enrichment.
- For example, an output of an industrial process may be a mixture including one or more amines including at least one tetramine, desirably at least one of L-TETA and TAEA if transamination techniques are used. Such mixture might even include a desired cyclic triamine such as some AEP. Such a mixture can be used as a reactant mixture in the practice of the invention to enrich the cyclic triamine content. As just one example, an illustrative output of an industrial process might include ethylenediamine (EDA), piperazine (PIP), diethylenetriamine (DETA), AEP, L-TETA, N-(Piperazinoethyl)ethylenediamine (PEEDA), Tetraethylenepentamine (L-TEPA), and others. This mixture can be processed in the practice of the present invention to increase the AEP content. Optionally, one or more of the amines of such a starting mixture, including the AEP, can be removed prior to being subjected to the transamination reaction. Examples of enriching the AEP content of such a mixture and other mixtures in the context of both transamination and reductive amination are provided below. Some of the amine constituents of such a mixture can react to make higher amines. These higher amines can ring close to yield a cyclic triamine such as AEP and a by-product such as ammonia or an amine.
- The reaction mixture for transamination can be contacted with catalyst at temperatures of from 130°C to 170°C for transamination. Below the preferred temperature ranges, the conversion to cyclic triamine may be too slow to be practical for commercial scale production. Above the preferred temperature ranges, selectivity may be reduced to an undue degree, increasing the yield of by-products. In some instances, such by-products may have commercial value and be desirable as a consequence. In other instances, by-products constitute impurities as a practical matter.
- Similarly, the reaction mixture for transamination is contacted with catalyst at pressure(s) in the range of 400 psi (2,758 kPa) to 800 psi (5,516 kPa). Preferably, the pressure is sufficient to maintain the reactor contents in a liquid state as the reaction proceeds. In many instances, the pressure will vary as the reaction proceeds. For instance, ammonia is a by-product of a typical transamination process. The production of ammonia causes the pressure generally to increase as the reaction proceeds. Ammonia and/or other pressure-increasing products can be removed from the reactor in order to keep the pressure below a desired threshold.
- In one mode of practice, precursors can be converted into suitable starting materials, which are then converted to cyclic triamines via transamination reactions. According to one approach, an amine or a mixture of amines can be alkoxylated to form starting materials. For example, a stream containing EDA and DETA can be ethoxylated to give a mixture including symmetrical and/or unsymmetrical DiHEED and linear and/or branched hydroxyethyl DETA. These product intermediates can be converted to cyclic triamines as described herein using transamination techniques.
- The following Assignee co-pending applications filed co-currently herewith describe technology relating to catalysts, reductive amination, and/or transamination. Each is incorporated herein by reference in its respective entirety for all purposes.
- 1. 1. Attorney Docket Number 66049 (DOW0015/P1) titled "LOW METAL LOADED, ALUMINA SUPPORTED, CATALYST COMPOSITIONS AND AMINATION PROCESS" by Stephen W. King et al.
- 2. 2. Attorney Docket Number 67688 (DOW0016/P1) titled "LOW METAL CATALYST COMPOSITIONS INCLUDING ACIDIC MIXED METAL OXIDE AS SUPPORT" by Steven W. King et al.
- 3. 3. Attorney Docket Number 67687 (DOW0018P1) titled "A PROCESS TO SELECTIVELY MANUFACTURE DIETHYLENETRIAMINE (DETA) OR OTHER DESIRABLE ETHYLENAMINES VIA CONTINUOUS TRANSAMINATION OF ETHYLENEDIAMINE (EDA), AND OTHER ETHYLENEAMINES OVER A HETEROGENEOUS CATALYST SYSTEM" by Ronald Gary Cook et al.
- 4. 4. Attorney Docket Number 67691 (DOW0019P1) titled "METHODS FOR MAKING ETHANOLAMINE(S) AND ETHYLENEAMINE(S) FROM ETHYYLENE OXIDE AND AMMONIA, AND RELATED METHODS" by David Do et al.
- 5. 5. Attorney Docket Number 67686 (DOW0021/P1) titled "Method Of Manufacturing EthyleneaminES" by David M. Petraitis et al.
- The present invention will now be further described with reference to the following illustrative examples.
- A catalyst was prepared by an incipient wetness technique using two impregnations. A solution of 107.6 grams of nickel nitrate hexahydrate (Aldrich no. 244074; crystal, 98%) and 8.26 grams of ammonium perrhenate (Molymet) in 318 ml deionized water was prepared. The solution was heated to 70°C. 193 ml of the solution was added to 297.0 grams of a pre-dried alumina/silica carrier (Al2O3/SiO2, 80:20, 1/16" extrudate, SA=153 m2/g), followed by calcination in air at 340°C for 2 hours. A second impregnation using the remaining solution (188 ml) was followed by calcination at 340°C for 3 hours. The catalyst was reduced at 340°C in flowing hydrogen at a flow rate of ∼1600 cc/min for three hours. Following the reduction, the catalyst was allowed to cool to room temperature and passivated using 1% oxygen in nitrogen to allow handling in air. The final yield was 325.5 grams of catalyst with a nominal composition of 6.8 wt. % nickel and 1.8 wt. % rhenium on alumina-silica.
- The catalyst was used to convert L-TETA to AEP. The L-TETA was supplied in a reaction mixture including other amines per Table A. Seven runs were performed at different, respective temperatures ranging from 120°C to 155°C. Each reaction took place over 295 grams of catalyst described above loaded into 86.25" of 0.688" ID stainless steel tubing. A temperature traverse from 120-155°C was conducted with an amine feed rate of 500∼1000 gmole/hr/kg-cat-, and H2 flow at 9-10 slph (about 10x hydrogen necessary to saturate the feed). All testing was done at 800 psig. The liquid product was collected in a receiver, the ammonia was weathered off and the product mix analyzed by capillary gas chromatography.
Table A Temp, °C: 120 135 144 154 155 150 145 GC results, wt% Run no. Feed 1 2 3 4 5 6 7 EDA 0 0.2107 0.5494 0.9096 1.8311 1.7375 1.3635 0.8512 Piperazine 0.008 0.0412 0.2568 1.8161 5.5513 5.2866 3.3932 1.6659 DETA 4.1921 4.2671 4.2836 4.3508 3.6426 3.6183 4.2096 4.3645 4EP 11.0877 12.2184 13.5185 20.3779 34.3297 33.3863 26.3092 19.5101 L-*TETA 71.8928 71.1804 69.1141 54.6221 26.891 27.545 42.3373 55.7212 PEEDA 1.0527 1.1101 1.3597 2.8451 7.7807 7.4208 0.043 0.0159 L-TEPA 7.9535 7.9258 8.098 8.296 6.8927 6.816 8.0667 8.1914 Other Amines 3.81 3.05 2.82 6.79 13.09 14.19 14.28 9.68 - As the table shows conversion of L-TETA produces a significant amount of AEP in the resultant product mix. As conversion levels increase AEP and other materials convert to higher ethyleneamines.
- Various materials were also evaluated in a batch mode as reported in this and the ensuing examples unless otherwise expressly noted. The reactions were conducted in a 2L high-pressure 316SS autoclave (Autoclave Engineers) equipped with a magnetic stirrer, a dip tube for sampling, and a catalyst basket. Catalyst of Example 1 was charged to the catalyst basket and activated overnight with flowing hydrogen at 180°C. The autoclave was cooled to room temperature, and the liquid reactants charged by pressure, followed by ammonia (optional), taking care not to admit air. The autoclave was brought to operating pressure with hydrogen, and heated to operating temperature with stirring. Pressure was adjusted during the run, if necessary, by bleeding off or adding hydrogen to the autoclave. Samples were taken hourly via the dip tube and analyzed by GC. Prior to analysis, ammonia (if present) was weathered off.
- Table 1 gives the results from reacting 900 grams of EDA with 100 grams of a Ni/Re catalyst at 160 C and an initial hydrogen pressure of 100 psig. The pressure of the reactor during the run was 170 to 730 psig. As can be seen from the table, AEP increases with EDA conversion, but still represents only a small portion (< 5 percent) of the product mix even at high EDA conversion. Still, the amount of AEP in the product mix was enriched by almost 300% relative to the reactant mixture. On an industrial scale, depending on the size of the commercial unit, this can result in a significant amount of extra pounds of AEP on an annual basis.
Table 1 Catalyst: Ni/Re (6.8/1.8 wt.%) on alumina/silica 80:20 Run no. 1 2 3 4 5 Time, hrs 2 3 4 5 6 Temp, °C 160 159 162 162 162 GC results EDA 73.92 65.14 57.61 50.68 45.20 PIP 8.03 11.14 14.07 17.29 19.58 DETA 13.39 16.79 19.31 20.68 21.33 AEP 1.16 2.03 2.88 3.78 4.83 I-TETA 1.52 2.27 3.03 3.63 4.14 PEEDA 0.20 0.35 0.51 0.74 1.06 I-TEPA 0.26 0.47 0.63 0.85 1.04 OTHERS 1.53 1.81 1.98 2.35 2.82 ∼EDA Conversion,% 29.41 38.79 46.63 53.65 59.05 Wt% in Product (EDA free) PIP 30.79 31.96 33.19 35.06 35.74 DETA 51.35 48.18 45.55 41.93 38.93 AEP 4.44 5.82 6.78 7.67 8.82 I-TETA 5.84 6.52 7.14 7.36 7.55 Other Amines 7.59 7.53 7.34 7.98 8.96 100.00 100.00 100.00 100.00 100.00 - Table 2 gives the results from reacting 844 grams of EDA with 100 grams of a commercial nickel on silica/alumina catalyst at 145-158°C and an initial hydrogen pressure of 270 psig but otherwise using the procedures of Example 2. The pressure of the reactor during the run was 800 to 1135 psig. As can be seen from the table, AEP increases with EDA conversion. These conditions produced less AEP at a given EDA conversion than those in Table 1 above.
Table 2 Catalyst: Sud-Chemie C46-7-03, 50% Ni on silica/alumina Run no. 1 2 3 4 5 6 Time, hrs 1 2 3 4 5 6 Temp, °C 156 152 154 145 147 158 GC results EDA 91.91 80.96 77.02 70.97 63.51 54.66 PIP 0.29 1.27 1.93 3.20 5.46 9.09 DETA 7.24 15.34 17.67 20.67 23.47 25.10 AEP 0.01 0.07 0.11 0.21 0.49 1.07 I-TETA 0.40 1.72 2.34 3.45 4.82 6.37 PEEDA 0.01 0.02 0.03 0.07 0.17 0.44 I-TEPA 0.09 0.53 0.76 1.20 1.62 2.30 OTHER AMINES 0.06 0.10 0.13 0.22 0.46 0.98 ∼EDA Conversion,% 9.46 21.84 26.20 32.80 40.75 49.87 Wt% in Product (EDA free) PIP 3.53 6.65 8.38 11.01 14.97 20.05 DETA 89.46 80.57 76.91 71.22 64.33 55.37 AEP 0.10 0.35 0.48 0.73 1.34 2.36 I-TETA 4.97 9.03 10.20 11.88 13.20 14.04 Other Amines 1.93 3.38 4.03 5.16 6.17 8.18 100.00 100.00 100.00 100.00 100.00 100.00 - Table 3 gives the results from reacting 740 grams of EDA with 100 grams of a commercial nickel on silica catalyst at 160-185°C and an initial hydrogen pressure of 236 psig but otherwise using the procedures of Example 2. The pressure of the reactor during the run was 960 to 2140 psig. As can be seen from the table, AEP increases with EDA conversion. These conditions produced more AEP at a given EDA conversion than those in Table 2, but less than the process conditions for Table 1.
Table 3 Catalyst: Engelhard Ni-5256E 57% Ni on silica 1/8" extrudate Run no. 1 2 3 4 5 6 7 Time, hrs 1 2 3 4 5 6 7 Temp, °C 166 160 173 175 181 180 184 GC results EDA 70.80 71.44 69.09 68.10 66.56 63.90 59.64 PIP 5.74 5.72 6.19 6.73 7.35 8.50 9.91 DETA 16.56 15.83 17.85 18.07 17.89 18.70 20.77 AEP 0.98 0.93 1.08 1.21 1.29 1.56 2.03 I-TETA 3.16 3.20 3.45 3.53 3.78 4.01 4.45 PEEDA 0.50 0.57 0.53 0.57 0.72 0.80 0.84 I-TEPA 1.02 1.31 1.10 1.04 1.38 1.36 1.25 OTHER AMINES 1.24 1.00 0.71 0.75 1.04 1.17 1.11 ∼EDA Conversion,% 32.82 32.19 34.73 35.78 37.40 40.18 44.62 Wt% in Product (EDA free) PIP 19.65 20.04 20.04 21.09 21.98 23.54 24.55 DETA 56.74 55.41 57.74 56.65 53.48 51.80 51.47 AEP 3.36 3.27 3.49 3:79 3.85 4.33 5.04 I-TETA 10.81 11.19 11.17 11.07 11.32 11.10 11.03 Other Amines 9.43 10.10 7.57 7.39 9.38 9.22 7.92 - Table 4 gives the results from reacting 800 grams of EDA with 100 grams of a commercial nickel on silica catalyst at 179-180°.C and an initial hydrogen pressure of 40 psig but otherwise using the procedures of Example 2. The pressure of the reactor during the run was 650 to 1000 psig. As can be seen from the table, AEP increases with EDA conversion. Comparing these results with Table 3 which uses the same catalyst, shows these conditions at an initial lower hydrogen concentration produced more AEP at a given EDA conversion than process conditions for Table 3.
Table 4 Catalyst: Engelhard Ni-5256E 57% Ni on silica 1/8" extrudate Run no. 1 2 3 4 Time, hrs 1 2 3 4 Temp, °C 179 180 180 180 GC results EDA 64.78 49.98 38.25 34.26 PIP 12.21 18.39 23.26 24.92 DETA 13.14 17.03 19.68 17.99 AEP 2.64 4.82 7.04 7.88 I-TETA 1.92 2.91 3.68 3.55 PEEDA 0.86 1.38 1.88 2.50 I-TEPA 0.53 0.76 0.62 0.82 OTHER AMINES 3.92 4.73 5.60 8.08 ∼EDA Conversion,% 38.87 54.05 65.54 69.20 Wt% in Product (EDA free) PIP 34.67 36.78 37.67 37.91 DETA 37.32 34.04 31.87 27.36 AEP 7.50 9.64 11.40 11.98 I-TETA 5.46 5.82 5.96 5.40 - The data in tables I through 4 show that converting EDA to AEP is challenging, even when using a preferred catalyst and practicing principles of the present invention. It is believed that one factor contributing to this difficulty is that much of the DETA present initially and/or formed as a reaction product is converted to PIP, making further reaction difficult. This hypothesis is borne out by the following example, where the feed includes more DETA at the outset. The example shows that starting out with a higher amine than EDA does not necessarily simplify the route to AEP.
- Table 5 gives the results from reacting 802 grams of a mixed EDA/DETA with 100 grams of a Ni/Re on alumina/silica (80:20) catalyst at 150-155°C at an initial hydrogen pressure of 150 psig but otherwise using the procedures of Example 2. The pressure of the reactor during the run was 215 to 670 psig. As can be seen from the table,AEP increases with EDA conversion. Comparing these results with Tables 1-4 above shows this feed does not produce a significant increase in AEP in the final product mix
Table 5 Catalyst: Ni/Re (6.8/1.8 wt.%) on alumina/silica 80:20 Run no. Feed 1 2 3 4 5 6 7 8 Time, hrs 1 2 3 4 5 6 7 8 Temp,°C 150 150 150 150 150 155 155 155 ∼EDA Conversion, % 14.36 15.39 23.59 30.48 35.25 39.72 46.70 52.59 GC results, Wt% EDA 64.28 55.05 54.39 49.12 44.69 41.63 38.75 34.26 30.48 PIP 0.06 3.49 3.88 6.14 8.30 10.48 13.55 16.71 20.10 DETA 35.57 36.74 37.07 37.72 37.36 36.45 34.50 31.17 33.59 AEP 0.04 0.27 0.36 0.64 0.94 1.27 1.64 2.44 3.22 I-TETA 0.00 3.33 3.35 4.94 6.26 7.24 8.11 9.31 9.82 PEEDA 0.00 0.04 0.04 0.09. 0.01 0.02 0.42 0.63 0.96 I-TEPA 0.00 0.60 0.46 0.87 1.20 1.39 1.83 2.06 2.36 OTHER 0.05 0.47 0.46 0.49 1.24 1.52 1.19 1.00 1.90 AMINES total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 100.00 - Example 2 to 5 suggests adding more DETA would give more AEP. As shown here, starting with more DETA at the outset does not lead to significantly more production of AEP. It is believed that the DETA is converted to PIP, which essentially stops further reactions as a practical matter. This shows that using even higher amines having 4 or more amines per molecule as described in further examples provides a much more effective route to cyclic amines such as AEP. It is believed that these further routes are more effective because they proceed via ring closure and/or reduction mechanisms that proceed substantially through alternative immediates rather than PIP.
- Table 6 gives the results from reacting 800 grams of a mixed ethyleneamines feed which has a large percentage of linear TETA in the mix, with 100 grams of a commercial nickel on silica catalyst at 150-155°C in the absence of hydrogen but otherwise using the procedures of Example 2. The pressure of the reactor during the run was 286 to 730 psig. As can be seen from the table, AEP increases with feed conversion. Comparing these results with Tables 1-5 shows this feed produces a much more significant amount of AEP in the final product mix compared to when EDA or a mix of EDA/DETA is used as the feed.
Table 6 Catalyst: Sud-Chemie C46-7-03, 50% Ni on silica/alumina Run no. Feed 1 2 3 4 5 6 Time, hrs 1 2 3 4 5 6 Temp, °C 153 154 155 155 155 155 ∼I-TETA Conversion,% 28.29 51.22 68.83 84.34 92.66 96.80 GC results, Wt% EDA 0.00 0.99 1.50 1.86 1.97 1.82 1.49 PIP 0.00 1.63 2.76 4.25 6.07 7.39 8.36 DETA 0.06 1.50 1.64 1.67 1.35 0.96 0.09 AEP 0.64 13.11 24.11 31.89 38.60 41.85 43.06 I-TETA 80.97 58.06 39.49 25.24 12.68 5.94 2:59 PEEDA 3.70 6.28 8.71 10.94 13.58 15.46 16.68 I-TEPA 8.02 7.36 6.23 5.09 3.52 2.29 1.44 OTHER AMINES 6.61 11.07 15.54 19.06 22.23 24.29 26.30 total 100.00 100.00 100.00 100.00 100.00 100.00 100.00 - This example uses a commercially available TETA obtained from an EDC process. Table 7 shows the composition of the commercial product and gives the results from reacting 800 grams of the mixed ethyleneamines feed, which has a large percentage of linear TETA in the mix, with 100 grams of a commercial nickel on silica catalyst at 150°C and an initial hydrogen pressure of 36 psig but otherwise using the procedures of Example 2. The pressure of the reactor during the run was 186 to 613 psig. As can be seen from the table, AEP increases with feed conversion. Comparing these results with Tables 1-5 shows this feed produces a much more significant amount of AEP in the final product mix compared to when EDA or EDA/DETA is used as the feed. However, it produces a lower amount of AEP in the final product mix than the process in Table 6 due to the lower amount of linear TETA in the feed.
Table 7 Catalyst: Sud-Chemie C46-7-03, 50% Ni on silica/alumina Run no. Feed 1 2 4 5 6 Time, hrs 1 2 4 5 6 Temp, °C 150 150 150 150 150 ∼I-TETA Conversion,% 43.52 64.52 78.14 88.92 95.57 GC results, Wt% EDA 0.05 1.03 1.54 1.74 1.51 1.25 PIP 0.01 1.84 3.64 4.96 5.38 6:30 DETA 0.14 1.41 1.69 1.53 1.09 0.64 AEP 0.02 12.59 22.48 28.15 28.27 29.51 TAEA 4.48 1.75 0.74 0.32 0.11 0.03 I-TETA 59.61 33.67 21.15 13.03 6.61 2.64 DAEP 12.63 12.20 12.57 12.42 10.65 9.66 PEEDA 20.48 20.63 22.58 23.58 21.30 20.60 I-TEPA 0.02 1.79 2.20 2.04 1.47 0.96 OTHER AMINES 2.56 13.10 11.40 12.22 23.61 28.41 total 100.00 100.00 100.00 100.00 100.00 100.00 - Table 8 gives the results from reacting 800 grams of TAEA, with 100 grams of a commercial nickel on silica catalyst at 150°C in the absence of hydrogen but otherwise using the procedures of Example 2. The pressure of the reactor during the run was 213 to 730 psig. As can be seen from the table, AEP increases with TAEA conversion. Comparing these results with Tables 1-7 show that TAEA produces significantly more AEP in the final product mix compared to when EDA, EDA/DETA, or feeds which have a high percentage of linear TETA is used as the feed.
Table 8 Catalyst: Sud-Chemie C46-7-03, 50% Ni on silica/alumina Run no. Feed 1 2 3 4 5 Time, hrs 1 2 3 4 5 Temp, °C 150 150 150 150 150 ∼TAEA Conversion,% 34.99 58.52 76.69 90.59 97.20 GC results, Wt% EDA 0.00 0.04 0.06 0.13 0.13 0.13 PIP 0.00 0.24 0.50 0.87 1.22 1.55 DETA 0.12 0.67 0.73 0.67 0.42 0.21 AEP 0.01 30.49 47.66 64.01 71.38 74.91 TAEA 97.11 63.13 40.28 22.64 9.14 2.72 I-TETA 0.01 0.02 0.02 0.04 0.27 0.35 DAEP 0.03 0.00 0.00 0.01 0.00 0.00 PEEDA 0.03 0.10 0.23 0.46 0.74 1.09 I-TEPA 0.13 0.07 0.04 0.02 0.01 0.01 OTHER AMINES 2.54 5.23 10.48 11.17 16.67 19.04 total 100.00 100.00 100.00 100.00 100.00 100.00
Claims (10)
- A method of making a cyclic triamine of the type comprising first and second nitrogen backbone atoms and an N-amino moiety pendant from at least one of the nitrogen backbone atoms, comprising the steps of:providing a polyfunctional compound comprising at least 4 amine moieties and, optionally, one or more nitrile moieties;causing the ring closure of the polyfunctional compound in the presence of a catalyst comprising at least Ni or Ni and Re at a temperature of from 130 °C to 170 °C and a pressure in the range of 400 psi (2,758 kPa) to 800 psi (5,516 kPa), to cause the polyfunctional compound to react with itself to form the cyclic amine.
- The method of claim 1, wherein the polyfunctional compound is a tetraamine.
- The method of claim 1, wherein the polyfunctional compound comprises one or more tetraamines.
- The method of making of claim 1, wherein the polyfunctional compound comprises at least one nitrile moiety.
- The method of any preceding claim, wherein the catalyst comprises both Ni and Re.
- The method of any preceding claim, wherein the catalyst is heterogeneous.
- The method of any preceding claim, wherein the selectivity for the conversion of the reactant to the cyclic triamine is at least 10 weight %.
- The method of any preceding claim, wherein the conversion of the reactant is at least 2 weight % of the polyfunctional compound.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US19541208P | 2008-10-06 | 2008-10-06 | |
PCT/US2009/005471 WO2010042159A1 (en) | 2008-10-06 | 2009-10-06 | Methods of making cyclic, n-amino functional triamines |
Publications (3)
Publication Number | Publication Date |
---|---|
EP2356095A1 EP2356095A1 (en) | 2011-08-17 |
EP2356095B1 EP2356095B1 (en) | 2013-11-20 |
EP2356095B2 true EP2356095B2 (en) | 2017-09-27 |
Family
ID=41467155
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09744802.1A Active EP2356095B2 (en) | 2008-10-06 | 2009-10-06 | Methods of making cyclic, n-amino functional triamines |
EP09789399.4A Active EP2356096B1 (en) | 2008-10-06 | 2009-10-06 | Methods of making cyclic, n-amino functional triamines |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP09789399.4A Active EP2356096B1 (en) | 2008-10-06 | 2009-10-06 | Methods of making cyclic, n-amino functional triamines |
Country Status (7)
Country | Link |
---|---|
US (3) | US8273884B2 (en) |
EP (2) | EP2356095B2 (en) |
JP (2) | JP5897904B2 (en) |
CN (2) | CN102227414B (en) |
BR (2) | BRPI0914009A2 (en) |
ES (2) | ES2444924T3 (en) |
WO (2) | WO2010042159A1 (en) |
Families Citing this family (23)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP5469173B2 (en) * | 2008-10-06 | 2014-04-09 | ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー | Low metal content, alumina supported catalyst composition and amination method |
JP2012504610A (en) * | 2008-10-06 | 2012-02-23 | ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー | Method for producing ethyleneamine |
CN103588646B (en) * | 2008-10-06 | 2016-04-13 | 陶氏环球技术有限责任公司 | Method and the methods involving of ethanolamines and ethylene amine is manufactured by oxyethane and ammonia |
JP5897904B2 (en) * | 2008-10-06 | 2016-04-06 | ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー | Method for producing cyclic, N-amino functional triamines |
WO2010042161A1 (en) | 2008-10-06 | 2010-04-15 | Union Carbide Chemicals & Plastics Technology Llc | Low metal (nickel and rhenium) catalyst compositions including acidic mixed metal oxide as support |
WO2010042160A1 (en) * | 2008-10-06 | 2010-04-15 | Union Carbide Chemicals & Plastics Technology Llc | A process to selectively manufacture diethylenetriamine (deta) or other desirable ethylenamines via continuous transamination of ethylenediamine (eda), and other ethyleneamines over a heterogeneous catalyst system |
EP2340240B1 (en) * | 2008-10-06 | 2014-07-23 | Union Carbide Chemicals & Plastics Technology LLC | Transalkoxylation of nucleophilic compounds |
CN101963754B (en) * | 2009-06-26 | 2012-12-19 | 罗门哈斯电子材料有限公司 | Methods of forming electronic device |
EP2638020B1 (en) | 2010-11-10 | 2016-09-07 | Dow Global Technologies LLC | Transamination of nitrogen-containing compounds to make cyclic and cyclic/acyclic polyamine mixtures |
BR112013011669A2 (en) | 2010-11-10 | 2019-09-24 | Dow Global Technologies Llc | method for making a mixture of products containing linear high molecular weight polyamine, method for making a mixture of high molecular weight polyamine congeners and method for making a mixture of high molecular weight acyclic polyamines |
EP2797902B1 (en) | 2011-12-29 | 2017-04-26 | Dow Global Technologies LLC | Compositions containing cyclic amine compounds, and polyurethane foams made therefrom |
CN104169262B (en) * | 2011-12-29 | 2017-04-26 | 陶氏环球技术有限责任公司 | Cyclic polyamine compound from cyclic polyamine compound formation higher molecular weight |
BR112014015972B1 (en) | 2011-12-29 | 2020-12-29 | Dow Global Technologies Llc | composition, polyether polyol amine, polyurethane foam, method for preparing a polyether polyol amine and method for preparing a polyurethane foam |
US20150246999A1 (en) * | 2012-10-24 | 2015-09-03 | Dow Global Technologies Llc | Ethyleneamine epoxy hardener |
WO2015084619A1 (en) | 2013-12-02 | 2015-06-11 | Dow Global Technologies Llc | Preparation of high molecular weight, branched, acyclic polyalkyleneamines and mixtures thereof |
EP3087217B1 (en) | 2013-12-27 | 2018-11-07 | Dow Global Technologies LLC | Corrosion inhibiting compositions including bis-imidazoline compounds derived from enriched linear tetramines |
EP3087220B1 (en) | 2013-12-27 | 2019-06-26 | Dow Global Technologies LLC | Method to treat textile with compositions including quaternary bis-imidazoline compounds derived from linear tetramines to improve moisture management and provide antimicrobial protection |
JP6671490B2 (en) * | 2016-02-12 | 2020-03-25 | ヌーリオン ケミカルズ インターナショナル ベスローテン フェノーツハップNouryon Chemicals International B.V. | Method for preparing higher ethylene amines and ethylene amine derivatives |
CN108713012B (en) * | 2016-02-12 | 2021-07-02 | 阿克苏诺贝尔化学品国际有限公司 | Process for preparing higher ethyleneamines and ethyleneamine derivatives |
BR112018014272B1 (en) * | 2016-02-12 | 2021-12-28 | Akzo Nobel Chemicals International B.V. | ETHYLENOAMINES PREPARATION PROCESS |
JP7235716B6 (en) * | 2017-07-10 | 2023-03-22 | ヌーリオン ケミカルズ インターナショナル ベスローテン フェノーツハップ | Method for preparing higher ethyleneamines or their urea derivatives |
TWI762669B (en) | 2017-07-10 | 2022-05-01 | 荷蘭商安科智諾貝爾化學國際公司 | Process for making higher ethylene amines |
SG11202001971UA (en) * | 2017-09-18 | 2020-04-29 | Chevron Oronite Co | Polyolefin dispersants and methods of making and using thereof |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3055901A (en) † | 1961-05-18 | 1962-09-25 | Jefferson Chem Co Inc | Preparation of aminoethylpiperazine |
US3285920A (en) † | 1964-01-16 | 1966-11-15 | Jefferson Chem Co Inc | Combination process for producing piperazine and triethylenediamine |
US3733325A (en) † | 1970-12-16 | 1973-05-15 | Jefferson Chem Co Inc | Preparation of aminoethylpiperazine |
EP0197612A2 (en) † | 1985-04-04 | 1986-10-15 | Union Carbide Corporation | Interchangeable process scheme |
Family Cites Families (120)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2861995A (en) | 1956-04-27 | 1958-11-25 | Dow Chemical Co | Process for the conversion of ethanolamine |
US3110732A (en) | 1959-12-18 | 1963-11-12 | Jefferson Chem Co Inc | Method for preparing basic polyether compositions |
GB1058304A (en) | 1964-03-12 | 1967-02-08 | Shell Int Research | Process for the purification of fluids |
US3394186A (en) | 1964-10-06 | 1968-07-23 | Jefferson Chem Co Inc | Manufacture of anhydrous ethylenediamine |
US3658692A (en) | 1969-10-28 | 1972-04-25 | Exxon Research Engineering Co | Preparation of white oils with aluminum-alkyl activated iron group metal catalysts |
US3847754A (en) | 1970-08-03 | 1974-11-12 | Ppg Industries Inc | Recovery of glycols from mixed glycol composition by distillation with acid treatment |
US4032411A (en) | 1973-03-07 | 1977-06-28 | Beroi Kemi Ab | Process for the preparation of ethylene diamine having low water content |
DE2439275B2 (en) | 1974-08-16 | 1978-09-21 | Basf Ag, 6700 Ludwigshafen | Process for the preparation of diethylenetriamine and triethylenetetramine from ethylenediamine |
US4264776A (en) | 1976-01-02 | 1981-04-28 | Monsanto Company | Production of secondary amines |
US4123462A (en) | 1976-01-07 | 1978-10-31 | Union Carbide Corporation | Amination process using nickel-rhenium catalysts |
US4073750A (en) | 1976-05-20 | 1978-02-14 | Exxon Research & Engineering Co. | Method for preparing a highly dispersed supported nickel catalyst |
US4209424A (en) | 1977-12-12 | 1980-06-24 | Societe Chimique de la Grande Paroisse, Azote et Products Chimiques | Catalyst for manufacturing amines from alcohols |
US4328370A (en) | 1979-03-15 | 1982-05-04 | The Dow Chemical Company | Ammonation of trialkanolamines |
IL57019A (en) | 1979-04-08 | 1983-09-30 | Imi Tami Institute Research | Manufacture of ethylene diamine from ethylene dihalide |
US4400539A (en) | 1981-09-30 | 1983-08-23 | Union Carbide Corporation | Process for the manufacture of ethylenediamine |
US4404405A (en) | 1981-09-30 | 1983-09-13 | Union Carbide Corporation | Process for the preparation of polyethylene polyamines |
US4729981A (en) | 1981-10-13 | 1988-03-08 | Shell Internationale Research Maatschappij B.V. | ROR-activated catalyst for synthesis gas conversion |
US4552961A (en) | 1982-04-30 | 1985-11-12 | Union Carbide Corporation | Preparation of polyalkylene polyamines using phosphorus amide catalyst |
US4568746A (en) | 1982-12-29 | 1986-02-04 | Union Carbide Corporation | Catalytic preparation of diethylenetriamine |
US4584405A (en) | 1983-04-18 | 1986-04-22 | Texaco Inc. | Activated carbon catalysts and preparation of linear polyethylene polyamines therewith |
SE457608B (en) | 1986-07-11 | 1989-01-16 | Berol Kemi Ab | PROCEDURES FOR PREPARING A RUTENIUM DUPPED NICKEL AND / OR COBULATE CATALYST ON A POROES METAL OXIDES BASIS AND USING THE CATALYST IN A HYDRADING AND / OR DEHYDRATION REACTION |
US4510263A (en) | 1983-10-17 | 1985-04-09 | W. R. Grace & Co. | Catalyst with high geometric surface area alumina extrudate and catalyst with high geometric surface area |
US4845296A (en) | 1983-12-13 | 1989-07-04 | Union Carbide Corporation | Process for preparing alkanolamines |
US4602091A (en) | 1984-01-25 | 1986-07-22 | Texaco Inc. | Production of ethylenediamine and N-aminoethylpiperazine from piperazine |
US4625030A (en) | 1984-05-23 | 1986-11-25 | Union Carbide Corporation | Potentiated nickel catalysts for amination |
CA1300144C (en) | 1985-04-04 | 1992-05-05 | Arthur R. Doumaux, Jr. | Conversion of oxygen-containing polyamines |
US4708945A (en) | 1985-12-31 | 1987-11-24 | Exxon Research And Engineering Company | Catalysts comprising silica supported on a boehmite-like surface, their preparation and use |
US4806517A (en) | 1986-01-21 | 1989-02-21 | Texaco Inc. | Method for making pelleted phosphated catalysts derived from group IVB transition metal oxides and catalysts thus prepared |
US4698427A (en) * | 1986-06-09 | 1987-10-06 | Texaco Inc. | Catalytic method for the conjoint manufacture of N-aminoethylpiperazine and tetraethylenepentamine |
JPH0830040B2 (en) | 1986-08-13 | 1996-03-27 | 東ソー株式会社 | Method for producing alkylene amines |
US4870044A (en) | 1987-03-12 | 1989-09-26 | Phillips Petroleum Company | Treated alumina material for fixed hydrofining beds |
GB8707304D0 (en) | 1987-03-26 | 1987-04-29 | Bp Chem Int Ltd | Chemical process |
US4801573A (en) | 1987-10-23 | 1989-01-31 | 501 Den Norske Stats Oljeslenskap A.S. | Catalyst for production of hydrocarbons |
US4922024A (en) | 1988-04-14 | 1990-05-01 | The Dow Chemical Company | Amination process employing group vib metal catalysts |
US4983735A (en) | 1988-07-20 | 1991-01-08 | The Dow Chemical Company | Preparation of alcohol-extended and amine-extended piperazines |
US4883826A (en) | 1988-07-27 | 1989-11-28 | The Dow Chemical Company | Tertiary amine-containing polyols prepared in a mannich condensation reaction using a mixture of alkanolamines |
US5030740A (en) | 1988-10-14 | 1991-07-09 | The Dow Chemical Company | Process for preparing linearly-extended polyalkylenepolyamines |
US4927931A (en) | 1988-11-01 | 1990-05-22 | The Dow Chemical Company | Preparation of alkyl-extended, alcohol-extended or amine-extended piperazines |
US4888316A (en) | 1988-11-21 | 1989-12-19 | Phillips Petroleum Company | Preparation of hydrotreating catalyst from spent catalyst |
US5166442A (en) | 1988-12-20 | 1992-11-24 | The Dow Chemical Company | Catalytic reforming of alkyleneamines |
US5410086A (en) | 1989-06-27 | 1995-04-25 | Burgess; Lloyd M. | Selective preparation of diethylenetriamine |
US5120815A (en) | 1989-06-29 | 1992-06-09 | The Dow Chemical Company | Tertiary amine-containing polyols prepared in a mannich condensation reaction using a mixture of alkanolamines |
US5225600A (en) | 1989-08-08 | 1993-07-06 | Union Carbide Chemicals & Plastics Technology Corporation | Amines catalysis using group VIB metal-containing condensation catalysts |
US5210306A (en) | 1989-08-08 | 1993-05-11 | Union Carbide Chemicals & Plastics Technology Corporation | Promoted amines catalysis |
US5225599A (en) | 1990-03-30 | 1993-07-06 | Union Carbide Chemicals & Plastics Technology Corporation | Selective production of linear triethylenetetramine and aminoethylethanolamine |
US5214215A (en) | 1990-03-30 | 1993-05-25 | Union Carbide Chemicals & Plastics Technology Corporation | Selective production of aminoethylethanolamine |
US5073635A (en) | 1990-06-22 | 1991-12-17 | The Dow Chemical Company | Process of preparing linearly-extended polyalkylenepolyamines employing metal silicate catalysts |
CA2051476A1 (en) | 1990-09-17 | 1992-03-18 | Yasushi Hara | Process for producing an ethylenamine |
US5214306A (en) | 1991-01-29 | 1993-05-25 | Sanyo Electric Co., Ltd. | Light emitting diode |
JP3066429B2 (en) * | 1991-07-31 | 2000-07-17 | 東ソー株式会社 | Method for producing ethyleneamine |
JP3092230B2 (en) * | 1991-07-31 | 2000-09-25 | 東ソー株式会社 | Method for producing ethyleneamine |
US5321160A (en) | 1991-07-31 | 1994-06-14 | Tosoh Corporation | Process for producing an ethylenamine |
US5256786A (en) * | 1992-03-02 | 1993-10-26 | The Dow Chemical Company | Catalytic reforming of cyclic alkyleneamines |
JP3412167B2 (en) | 1992-09-01 | 2003-06-03 | ダイヤニトリックス株式会社 | N-vinylformamide composition |
USH1447H (en) | 1992-11-20 | 1995-06-06 | E. I. Du Pont De Nemours And Company | Coated silica shells |
US5352835A (en) | 1993-02-08 | 1994-10-04 | Texaco Chemical Company | Supported catalysts for amination |
DE4325848A1 (en) | 1993-07-31 | 1995-02-02 | Basf Ag | Process for the preparation of N- (2-hydroxyethyl) piperazine |
US5362914A (en) | 1993-08-25 | 1994-11-08 | Texaco Chemical Inc. | Decolorization of polyethylene polyamines using cobalt/copper/chromium |
US5721305A (en) | 1993-12-14 | 1998-02-24 | Unichema Chemie B.V. | Polyglycerol production |
EP0737514B1 (en) * | 1993-12-22 | 2001-06-13 | Union Carbide Chemicals & Plastics Technology Corporation | Reductive amination processes for the selective production of aminoethylethanolamine |
DE69512381T2 (en) | 1993-12-22 | 2000-04-06 | Union Carbide Chem Plastic | Reductive amination for the selective production of aminoethylethanolamine |
US5565092A (en) | 1994-03-16 | 1996-10-15 | Exxon Chemical Patents Inc. | Halogen resistant hydrogenation process and catalyst |
US5567847A (en) | 1995-02-21 | 1996-10-22 | Air Products And Chemicals, Inc. | Disproportionation of amines to produce secondary amines |
US5817593A (en) | 1995-06-02 | 1998-10-06 | The Dow Chemical Company | Catalyst and process for producing amines |
US5851948A (en) | 1996-08-20 | 1998-12-22 | Hydrocarbon Technologies, Inc. | Supported catalyst and process for catalytic oxidation of volatile organic compounds |
US5935889A (en) | 1996-10-04 | 1999-08-10 | Abb Lummus Global Inc. | Catalyst and method of preparation |
SE513250C2 (en) | 1997-11-11 | 2000-08-07 | Akzo Nobel Nv | Amination process for the production of polyamines |
US6117814A (en) | 1998-02-10 | 2000-09-12 | Exxon Research And Engineering Co. | Titania catalysts their preparation and use in fischer-tropsch synthesis |
JP3154984B2 (en) | 1998-03-13 | 2001-04-09 | 株式会社日本触媒 | Method for producing dialkanolamine and catalyst used therefor |
US6235677B1 (en) | 1998-08-20 | 2001-05-22 | Conoco Inc. | Fischer-Tropsch processes using xerogel and aerogel catalysts by destabilizing aqueous colloids |
US6534441B1 (en) * | 1999-03-06 | 2003-03-18 | Union Carbide Chemicals & Plastics Technology Corporation | Nickel-rhenium catalyst for use in reductive amination processes |
US6222008B1 (en) | 1999-05-06 | 2001-04-24 | Shell Oil Company | Treatment of polymer solution with acid and ammonia to improve polymer color |
US6306795B1 (en) | 1999-09-07 | 2001-10-23 | Cytec Technology Corp. | Stable highly active supported copper based catalysts |
JP4638646B2 (en) | 1999-12-17 | 2011-02-23 | イー・アイ・デュポン・ドウ・ヌムール・アンド・カンパニー | Continuous process for the preparation of polytrimethylene ether glycol |
FR2804689B1 (en) | 2000-02-08 | 2002-03-15 | Inst Francais Du Petrole | PROCESS FOR THE SYNTHESIS OF HYDROCARBONS IN THE PRESENCE OF A CATALYST COMPRISING A GROUP VIII METAL SUPPORTED ON SILICA-ALUMIN |
US6977273B2 (en) | 2000-03-01 | 2005-12-20 | Institut Francais Du Petrole | Process for synthesising hydrocarbons in the presence of a catalyst comprising a group VIII metal supported on silica-alumina |
FR2810563B1 (en) | 2000-06-23 | 2002-12-27 | Centre Nat Rech Scient | METHODS OF ETHERIFICATION OF GLYCEROL, AND CATALYSTS FOR CARRYING OUT SAID METHODS |
US6576796B1 (en) | 2000-06-28 | 2003-06-10 | Basf Aktiengesellschaft | Process for the preparation of alkylamines |
US7769619B1 (en) | 2000-08-14 | 2010-08-03 | Imaging Portals, Inc. | Automated business machine management |
DE10059629A1 (en) | 2000-12-01 | 2002-06-06 | Basf Ag | Process for the production of ethanolamines |
RU2186761C1 (en) | 2001-02-27 | 2002-08-10 | Закрытое акционерное общество "Каустик" | Method of synthesis of diethylenetriamine |
EP1249440A1 (en) | 2001-04-10 | 2002-10-16 | Taiwan Styrene Monomer Corporation | Process for preparing linear alkylbenzenes |
DE10129908A1 (en) | 2001-06-21 | 2003-01-02 | Basf Ag | Process for the preparation of secondary amines from primary amines |
SE524126C2 (en) | 2001-07-24 | 2004-06-29 | Akzo Nobel Nv | Process for the preparation of diethylenetriamine and higher polyethylene polyamines by transamination of ethylenediamine |
US6800586B2 (en) | 2001-11-23 | 2004-10-05 | Engelhard Corporation | NOx reduction composition for use in FCC processes |
US6703343B2 (en) | 2001-12-18 | 2004-03-09 | Caterpillar Inc | Method of preparing doped oxide catalysts for lean NOx exhaust |
US6822008B2 (en) | 2002-09-06 | 2004-11-23 | Conocophillips Company | Fischer-Tropsch catalysts using multiple precursors |
US7341976B2 (en) | 2002-10-16 | 2008-03-11 | Conocophillips Company | Stabilized boehmite-derived catalyst supports, catalysts, methods of making and using |
RU2226188C1 (en) | 2002-10-25 | 2004-03-27 | Закрытое акционерное общество "Каустик" | Method of producing di- and polyamines |
RU2226189C1 (en) | 2002-10-25 | 2004-03-27 | Закрытое акционерное общество "Каустик" | Method for production of ethylenediamine and polyethylenepolyamines |
ES2327635T3 (en) | 2002-11-15 | 2009-11-02 | Akzo Nobel N.V. | PURIFICATION / DECOLORATION TREATMENT OF NITRILE FATS. |
DE10261195A1 (en) | 2002-12-20 | 2004-07-01 | Basf Ag | Process for the preparation of a symmetrical secondary amine |
WO2005012223A1 (en) | 2003-08-01 | 2005-02-10 | Basf Aktiengesellschaft | Method for producing ethylene-amines |
DE10335991A1 (en) | 2003-08-01 | 2005-02-24 | Basf Ag | Process for the preparation of ethylene amines |
CN1901992B (en) | 2003-09-26 | 2010-09-29 | 3M创新有限公司 | Catalysts, activating agents, support media, and related methodologies useful for making catalyst systems especially when the catalyst is deposited onto the support media using physical vapor depositi |
US7541310B2 (en) | 2003-10-16 | 2009-06-02 | Conocophillips Company | Silica-alumina catalyst support, catalysts made therefrom and methods of making and using same |
KR100542911B1 (en) | 2003-10-25 | 2006-01-11 | 한국과학기술연구원 | POX reforming structured catalyst of gasoline for fuel cell powered vehicle application, and method for preparing the structured catalyst |
US7067455B2 (en) | 2003-11-21 | 2006-06-27 | Conocophillips Company | Copper modified catalysts for oxidative dehydrogenation |
US7348293B2 (en) | 2003-12-05 | 2008-03-25 | Chevron U.S.A. Inc. | Homogeneous modified-alumina Fischer-Tropsch catalyst supports |
DE10359811A1 (en) | 2003-12-19 | 2005-07-21 | Basf Ag | A method for increasing the space-time yield (RZA) in a process for preparing a symmetrical secondary amine |
US7745369B2 (en) | 2003-12-19 | 2010-06-29 | Shell Oil Company | Method and catalyst for producing a crude product with minimal hydrogen uptake |
US7323100B2 (en) | 2004-07-16 | 2008-01-29 | Conocophillips Company | Combination of amorphous materials for hydrocracking catalysts |
US8003806B2 (en) | 2004-11-12 | 2011-08-23 | OSI Pharmaceuticals, LLC | Integrin antagonists useful as anticancer agents |
US20060104895A1 (en) | 2004-11-18 | 2006-05-18 | Saint-Gobain Ceramics & Plastics, Inc. | Transitional alumina particulate materials having controlled morphology and processing for forming same |
WO2006099716A1 (en) | 2005-03-24 | 2006-09-28 | University Of Regina | Catalysts for hydrogen production |
DE102005019373A1 (en) | 2005-04-26 | 2006-11-02 | Basf Ag | Preparation of ethylene amine, useful as e.g. solvent and stabilizers, comprises continuous reaction of ethylene oxide with ammonia on inorganic ion-exchanger, and continuous reaction of reaction product with ammonia |
CN101384542B (en) | 2006-02-14 | 2012-07-04 | 巴斯夫欧洲公司 | Process for the distillative separation of mixtures comprising monoethylene glycol and diethylentriamine |
US7981836B2 (en) | 2006-05-24 | 2011-07-19 | Uop Llc | Hydrothermally stable alumina |
RU2472772C2 (en) | 2007-03-01 | 2013-01-20 | Басф Се | Method of producing triethylene tetramine (teta) through ethylenediamine diacetonitrile (eddn) |
US7595276B2 (en) | 2007-07-30 | 2009-09-29 | Jgc Catalysts And Chemicals Ltd. | Catalytic composition for oxychlorination |
US8563778B2 (en) | 2008-01-03 | 2013-10-22 | Akzo Nobel N.V. | Process to prepare ethylene amines |
CN101215239B (en) * | 2008-01-16 | 2010-07-07 | 西安近代化学研究所 | Combined preparation method for ethylene diamine and aminoethylpiperazine |
US8216961B2 (en) | 2008-08-27 | 2012-07-10 | Korea University Research And Business Foundation | Nanoparticles including metal oxide having catalytic activity |
WO2010042161A1 (en) | 2008-10-06 | 2010-04-15 | Union Carbide Chemicals & Plastics Technology Llc | Low metal (nickel and rhenium) catalyst compositions including acidic mixed metal oxide as support |
JP2012504610A (en) | 2008-10-06 | 2012-02-23 | ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー | Method for producing ethyleneamine |
JP5469173B2 (en) | 2008-10-06 | 2014-04-09 | ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー | Low metal content, alumina supported catalyst composition and amination method |
CN103588646B (en) | 2008-10-06 | 2016-04-13 | 陶氏环球技术有限责任公司 | Method and the methods involving of ethanolamines and ethylene amine is manufactured by oxyethane and ammonia |
WO2010042160A1 (en) | 2008-10-06 | 2010-04-15 | Union Carbide Chemicals & Plastics Technology Llc | A process to selectively manufacture diethylenetriamine (deta) or other desirable ethylenamines via continuous transamination of ethylenediamine (eda), and other ethyleneamines over a heterogeneous catalyst system |
EP2340240B1 (en) | 2008-10-06 | 2014-07-23 | Union Carbide Chemicals & Plastics Technology LLC | Transalkoxylation of nucleophilic compounds |
JP5897904B2 (en) * | 2008-10-06 | 2016-04-06 | ユニオン カーバイド ケミカルズ アンド プラスティックス テクノロジー エルエルシー | Method for producing cyclic, N-amino functional triamines |
-
2009
- 2009-10-06 JP JP2011530066A patent/JP5897904B2/en not_active Expired - Fee Related
- 2009-10-06 WO PCT/US2009/005471 patent/WO2010042159A1/en active Application Filing
- 2009-10-06 CN CN200980147876.6A patent/CN102227414B/en active Active
- 2009-10-06 EP EP09744802.1A patent/EP2356095B2/en active Active
- 2009-10-06 BR BRPI0914009-3A patent/BRPI0914009A2/en not_active Application Discontinuation
- 2009-10-06 US US12/587,380 patent/US8273884B2/en active Active
- 2009-10-06 ES ES09744802.1T patent/ES2444924T3/en active Active
- 2009-10-06 BR BRPI0914016-6A patent/BRPI0914016A2/en not_active Application Discontinuation
- 2009-10-06 WO PCT/US2009/005477 patent/WO2010042165A2/en active Application Filing
- 2009-10-06 CN CN200980147469.5A patent/CN102227413B/en active Active
- 2009-10-06 JP JP2011530070A patent/JP5774992B2/en not_active Expired - Fee Related
- 2009-10-06 EP EP09789399.4A patent/EP2356096B1/en active Active
- 2009-10-06 US US12/587,338 patent/US8618108B2/en active Active
- 2009-10-06 ES ES09789399T patent/ES2433422T3/en active Active
-
2012
- 2012-07-13 US US13/548,425 patent/US8907088B2/en active Active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3055901A (en) † | 1961-05-18 | 1962-09-25 | Jefferson Chem Co Inc | Preparation of aminoethylpiperazine |
US3285920A (en) † | 1964-01-16 | 1966-11-15 | Jefferson Chem Co Inc | Combination process for producing piperazine and triethylenediamine |
US3733325A (en) † | 1970-12-16 | 1973-05-15 | Jefferson Chem Co Inc | Preparation of aminoethylpiperazine |
EP0197612A2 (en) † | 1985-04-04 | 1986-10-15 | Union Carbide Corporation | Interchangeable process scheme |
Non-Patent Citations (1)
Title |
---|
Sigma-Aldrich Catalogue, product specification for "I-TETA" † |
Also Published As
Publication number | Publication date |
---|---|
WO2010042159A1 (en) | 2010-04-15 |
US20100094007A1 (en) | 2010-04-15 |
BRPI0914009A2 (en) | 2015-07-28 |
EP2356095A1 (en) | 2011-08-17 |
EP2356096A2 (en) | 2011-08-17 |
US20120277435A1 (en) | 2012-11-01 |
WO2010042165A2 (en) | 2010-04-15 |
US8618108B2 (en) | 2013-12-31 |
BRPI0914016A2 (en) | 2015-07-28 |
EP2356096B1 (en) | 2013-08-14 |
JP2012504611A (en) | 2012-02-23 |
CN102227414A (en) | 2011-10-26 |
CN102227413A (en) | 2011-10-26 |
ES2444924T3 (en) | 2014-02-27 |
WO2010042165A3 (en) | 2010-08-05 |
US20100094008A1 (en) | 2010-04-15 |
US8907088B2 (en) | 2014-12-09 |
JP5897904B2 (en) | 2016-04-06 |
ES2433422T3 (en) | 2013-12-11 |
CN102227414B (en) | 2016-05-18 |
US8273884B2 (en) | 2012-09-25 |
EP2356095B1 (en) | 2013-11-20 |
CN102227413B (en) | 2014-11-05 |
JP2012504614A (en) | 2012-02-23 |
JP5774992B2 (en) | 2015-09-09 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
EP2356095B2 (en) | Methods of making cyclic, n-amino functional triamines | |
JP4938802B2 (en) | Process for producing ethyleneamine and ethanolamine from monoethylene glycol (MEG) | |
RU2470009C2 (en) | Method of producing triethylene tetraamine | |
JP5124486B2 (en) | Process for producing ethyleneamine and ethanolamine by hydroamination of monoethylene glycol and ammonia in the presence of a catalyst | |
EP3596039B1 (en) | Process for manufacturing chain-extended hydroxyethylethyleneamines, ethyleneamines, or mixtures thereof | |
KR102596991B1 (en) | Method for producing advanced ethylene amine | |
US9000217B2 (en) | Transamination of nitrogen-containing compounds to high molecular weight polyalkyleneamines | |
KR20100014695A (en) | Method for producing tetraethylenepentamine | |
EP2638020B1 (en) | Transamination of nitrogen-containing compounds to make cyclic and cyclic/acyclic polyamine mixtures | |
CN101273007B (en) | Method for producing ethylene amines | |
CN110997638A (en) | Process for preparing cyclic urea adducts of ethylene amine compounds | |
EP0375355A2 (en) | Process for the catalytic reforming of alkylene amines to linearly-extended polyalkylene polyamines | |
KR20200007050A (en) | Process for preparing cyclic urea adducts of ethyleneamine compounds | |
JP2018012659A (en) | Method for producing polyethylene polyamines | |
CA2029428A1 (en) | Preparation of alcohol-extended and amine-extended piperazines |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
17P | Request for examination filed |
Effective date: 20110506 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
DAX | Request for extension of the european patent (deleted) | ||
17Q | First examination report despatched |
Effective date: 20120903 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
GRAP | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOSNIGR1 |
|
INTG | Intention to grant announced |
Effective date: 20130726 |
|
GRAS | Grant fee paid |
Free format text: ORIGINAL CODE: EPIDOSNIGR3 |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: GB Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: REF Ref document number: 641544 Country of ref document: AT Kind code of ref document: T Effective date: 20131215 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: FG4D |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R096 Ref document number: 602009020245 Country of ref document: DE Effective date: 20140116 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2444924 Country of ref document: ES Kind code of ref document: T3 Effective date: 20140227 |
|
REG | Reference to a national code |
Ref country code: NL Ref legal event code: VDEP Effective date: 20131120 |
|
REG | Reference to a national code |
Ref country code: AT Ref legal event code: MK05 Ref document number: 641544 Country of ref document: AT Kind code of ref document: T Effective date: 20131120 |
|
REG | Reference to a national code |
Ref country code: LT Ref legal event code: MG4D |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: HR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 Ref country code: NL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 Ref country code: FI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 Ref country code: IS Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140320 Ref country code: NO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140220 Ref country code: LT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 Ref country code: SE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 Ref country code: AT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 Ref country code: LV Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: PT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140320 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: EE Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R026 Ref document number: 602009020245 Country of ref document: DE |
|
PLBI | Opposition filed |
Free format text: ORIGINAL CODE: 0009260 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: RO Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 Ref country code: PL Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 Ref country code: CZ Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 Ref country code: SK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 |
|
26 | Opposition filed |
Opponent name: BASF SE Effective date: 20140801 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: DK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 |
|
PLAX | Notice of opposition and request to file observation + time limit sent |
Free format text: ORIGINAL CODE: EPIDOSNOBS2 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R026 Ref document number: 602009020245 Country of ref document: DE Effective date: 20140801 |
|
PLBB | Reply of patent proprietor to notice(s) of opposition received |
Free format text: ORIGINAL CODE: EPIDOSNOBS3 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SI Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MC Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 Ref country code: LU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20141006 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20141006 |
|
REG | Reference to a national code |
Ref country code: IE Ref legal event code: MM4A |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20141006 Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20141031 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20141031 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20150630 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20141031 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20141006 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20150915 Year of fee payment: 7 |
|
RIC2 | Information provided on ipc code assigned after grant |
Ipc: C07D 241/04 20060101AFI20150930BHEP Ipc: C07D 295/13 20060101ALI20150930BHEP |
|
APAH | Appeal reference modified |
Free format text: ORIGINAL CODE: EPIDOSCREFNO |
|
APBM | Appeal reference recorded |
Free format text: ORIGINAL CODE: EPIDOSNREFNO |
|
APBP | Date of receipt of notice of appeal recorded |
Free format text: ORIGINAL CODE: EPIDOSNNOA2O |
|
APBU | Appeal procedure closed |
Free format text: ORIGINAL CODE: EPIDOSNNOA9O |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20151026 Year of fee payment: 7 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: SM Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: BG Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 Ref country code: CY Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 Ref country code: GR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20140221 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MT Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 Ref country code: HU Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO Effective date: 20091006 Ref country code: TR Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 |
|
PUAH | Patent maintained in amended form |
Free format text: ORIGINAL CODE: 0009272 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: PATENT MAINTAINED AS AMENDED |
|
27A | Patent maintained in amended form |
Effective date: 20170927 |
|
AK | Designated contracting states |
Kind code of ref document: B2 Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO SE SI SK SM TR |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R102 Ref document number: 602009020245 Country of ref document: DE |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20161006 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20170927 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20161007 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: MK Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT Effective date: 20131120 |
|
REG | Reference to a national code |
Ref country code: DE Ref legal event code: R081 Ref document number: 602009020245 Country of ref document: DE Owner name: UNION CARBIDE CORPORATION, SEADRIFT, US Free format text: FORMER OWNER: UNION CARBIDE CHEMICALS & PLASTICS TECHNOLOGY LLC, MIDLAND, MICH., US Ref country code: DE Ref legal event code: R082 Ref document number: 602009020245 Country of ref document: DE Representative=s name: MURGITROYD & COMPANY, DE |
|
P01 | Opt-out of the competence of the unified patent court (upc) registered |
Effective date: 20230525 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20230830 Year of fee payment: 15 |